CN114481370A - Graphite-doped polyacrylonitrile-based nano composite material and preparation method and application thereof - Google Patents
Graphite-doped polyacrylonitrile-based nano composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114481370A CN114481370A CN202210182895.XA CN202210182895A CN114481370A CN 114481370 A CN114481370 A CN 114481370A CN 202210182895 A CN202210182895 A CN 202210182895A CN 114481370 A CN114481370 A CN 114481370A
- Authority
- CN
- China
- Prior art keywords
- graphite
- polyacrylonitrile
- doped
- doped polyacrylonitrile
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
The invention belongs to the technical field of new materials, and relates to a graphite-doped polyacrylonitrile-based nano composite material as well as a preparation method and application thereof. The preparation method comprises the following steps: mixing acrylonitrile monomer, carbonaceous material additive, initiator and molecular weight regulator, and heating to initiate polymerization to obtain the final product; the carbonaceous material additive is graphite, and mechanical stirring and ultrasonic treatment are carried out in the heating polymerization process, wherein the graphite is crystalline flake graphite or a derivative of the crystalline flake graphite. The invention takes graphite as the carbonaceous material additive, realizes the optimization of the carbon fiber graphite structure and the improvement of the mechanical property, can reduce the cost and is easy for industrialized popularization.
Description
Technical Field
The invention belongs to the technical field of new materials, and relates to a graphite-doped polyacrylonitrile-based nano composite material as well as a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
According to the research of the inventor, in order to optimize the structure of the carbon fiber, carbonaceous material additives are generally required to be added, the additives have relatively excellent mechanical properties, can be used as rigid fillers to prevent the crack in the fiber from expanding, and the interaction between the additives and the fiber matrix is beneficial to the stress transfer between the matrix and the fillers, so that the strength of the fiber is enhanced. In addition, the carbon material has a relatively perfect graphite lattice structure, can play a role of a nucleating agent in the preparation process of the carbon fiber, induces the formation and perfection of the graphitized lattice structure in the fiber, and is continuously close to the ideal structure of the carbon fiber. However, the inventors found that the existing carbonaceous material additives are generally graphene, carbon nanotubes, and the like, and the production process of these carbonaceous material additives is complicated and too expensive, and thus it is difficult to industrially popularize these carbonaceous material additives.
Disclosure of Invention
In order to solve the defects of the prior art, in the early research process, graphite is adopted to replace graphene, carbon nanotubes and the like as additives of carbonaceous materials, the structure of carbon fibers is optimized, the cost is reduced, and the industrial popularization is realized.
However, in the previous research, the present invention found that if only graphite is directly introduced into a spinning system as a carbonaceous material additive instead of graphene, carbon nanotubes, etc. to prepare carbon fibers or carbon nanofibers, the mechanical properties of the product will not only not increase, but also decrease, because the graphite has a larger size, and is easily agglomerated during the spinning process, and the agglomeration of the large-sized additive will reduce the dispersibility of graphite in the fiber matrix, weaken the interaction between the graphite additive and the fiber matrix, and easily develop into defect structures such as holes, cracks, etc. in the final carbon fibers or carbon nanofibers, thereby greatly damaging the mechanical properties of the fibers.
In order to solve the problems, the invention aims to provide a graphite-doped polyacrylonitrile-based nano composite material and a preparation method and application thereof.
On the one hand, the preparation method of the graphite-doped polyacrylonitrile-based nano composite material is that acrylonitrile monomer, carbonaceous material additive, initiator and molecular weight regulator are mixed and heated to initiate free radical polymerization, thus obtaining the graphite-doped polyacrylonitrile-based nano composite material; the carbonaceous material additive is graphite, mechanical stirring and ultrasonic treatment are carried out in the polymerization process, and the graphite is crystalline flake graphite or a derivative of the crystalline flake graphite.
The invention carries out mechanical stirring and ultrasonic treatment in the free radical polymerization process, realizes the uniform dispersion of graphite in acrylonitrile monomers through the synergistic action of the mechanical stirring and the ultrasonic treatment, avoids the agglomeration phenomenon of graphite particles, and directly realizes the good dispersion of the graphite in the polyacrylonitrile matrix after the polymerization is finished.
On the other hand, the graphite-doped polyacrylonitrile-based nano composite material is prepared by the preparation method.
In a third aspect, the application of the graphite-doped polyacrylonitrile-based nano composite material in the preparation of carbon fibers or carbon nano fibers can directly prepare the carbon fibers or the carbon nano fibers with uniformly dispersed graphite by dissolving the nano composite material and then carrying out gel spinning or electrostatic spinning.
The invention has the beneficial effects that:
1. in view of the fact that graphite is larger in size and smaller in specific surface area, slight agglomeration can develop into a defect structure in final carbon fibers or carbon nanofibers, in order to achieve uniform dispersion of a graphite additive, the method adopts a mode of combining ultrasound and stirring in the process of preparing the polyacrylonitrile-based nanocomposite material doped with graphite, the uniform dispersion of graphite is basically achieved, the finally obtained composite material is of a core-shell structure, the inner core is single unagglomerated graphite or graphite derivative particles, the outer shell is polyacrylonitrile, the polymer outer shell isolates the interaction between graphite, the accumulation tendency of the graphite is reduced, and the method is beneficial to achieving the addition of high-concentration graphite.
2. The flake graphite adopted in the invention has wide sources, very low price and simple preparation process, and can be matched with graphite raw materials with corresponding sizes according to the diameter of the required fiber, in addition, compared with graphene and carbon nano tubes, the flake graphite has certain structural rigidity, and the flake graphite can maintain a planar structure while being oriented along a fiber axis under the action of a drafting force in the spinning process, so that a fiber matrix is induced to grow a larger graphite lattice structure along the plane of the fiber matrix, and the graphene and the carbon nano tubes are easy to twist and wind in the fiber matrix, which can cause defect structures in the fiber, and the morphology of the graphene and the carbon nano tubes in the fiber matrix needs to be controlled by an additional process. Therefore, the graphite-doped polyacrylonitrile-based nano composite material provided by the invention has lower cost and simpler operability.
3. The polyacrylonitrile-based nano composite material doped with graphite prepared by the invention has simple preparation process and high production efficiency, directly realizes uniform mixing of polyacrylonitrile and graphite, and effectively avoids the situations of difficult and uneven graphite dispersion caused by entanglement of polyacrylonitrile molecular chains under the condition of direct mixing of the polyacrylonitrile and the graphite.
4. The polyacrylonitrile-based nano composite material doped with graphite prepared by the invention can be used as a precursor of carbon fiber for spinning, a spinning solution in which polyacrylonitrile and graphite particles are uniformly mixed is directly obtained after the composite material is dissolved, polyacrylonitrile-based carbon nano fiber or carbon fiber uniformly doped with graphite particles can be obtained by an electrostatic spinning or solution spinning method, the graphite particles can limit the expansion of cracks in a fiber matrix, meanwhile, the graphite particles have a graphite lattice mechanism which is the same as that of an ideal carbon fiber, and can be used as a template to induce the fiber matrix to be gradually converted into a lattice structure which is the same as that of the ideal carbon fiber in the pre-oxidation and carbonization processes, so that the comprehensive performance of the carbon fiber is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron microscope photograph of composite particles of polyacrylonitrile incompletely coated crystalline flake graphite obtained by aqueous phase precipitation polymerization in example 3 of the present invention.
FIG. 2 is a scanning electron microscope photograph of composite particles of crystalline flake graphite completely coated with polyacrylonitrile obtained by aqueous phase precipitation polymerization in example 1 of the present invention.
Fig. 3 is a scanning electron microscope photograph of the crystalline flake graphite doped carbon nanofiber prepared from the composite material obtained in example 2 in example 4 of the present invention.
Fig. 4 is a tensile stress contrast diagram of crystalline flake graphite doped carbon nanofibers prepared from the composite materials obtained in examples 1, 2 and 3 in example 4 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the problems of high cost and the like of graphene, carbon nanotubes and the like serving as carbonaceous material additives, the invention provides a graphite-doped polyacrylonitrile-based nanocomposite material and a preparation method and application thereof.
The invention provides a typical implementation mode of a preparation method of a graphite-doped polyacrylonitrile-based nano composite material, which comprises the steps of mixing an acrylonitrile monomer, a carbonaceous material additive, an initiator and a molecular weight regulator, and heating to initiate free radical polymerization to obtain the graphite-doped polyacrylonitrile-based nano composite material; the carbonaceous material additive is graphite, mechanical stirring and ultrasonic treatment are carried out in the polymerization process, and the graphite is crystalline flake graphite or a derivative of the crystalline flake graphite.
According to the invention, mechanical stirring and ultrasonic treatment are carried out in the heating polymerization process, and the graphite is uniformly dispersed among acrylonitrile monomers under the synergistic action of the mechanical stirring and the ultrasonic treatment, so that slight agglomeration is avoided, and the elimination of the agglomeration can avoid the generation of defect structures in subsequently prepared graphite doped carbon fibers or carbon nano fibers, so that the graphite replaces graphene, carbon nano tubes and the like as carbon material additives to optimize the structure of the carbon fibers.
The derivative of the flake graphite is various derivatives taking the flake graphite as a matrix, such as graphite oxide, expandable graphite, graphite fluoride and the like.
In some embodiments, the graphite has a particle size of 0.1 to 100 μm.
In some embodiments, the graphite is added in an amount of 0.1 to 5 wt% based on the mass of acrylonitrile.
In some embodiments, the initiator is added in an amount of 0.01 to 10 wt% based on the mass of acrylonitrile.
In some embodiments, the polymer is prepared using an aqueous precipitation polymerization process. The preparation method is simpler, and the production efficiency is further improved.
In some embodiments, the initiator is ammonium persulfate or an ammonium persulfate-ammonium sulfite composite initiation system.
In some embodiments, the polymerization temperature is 40 to 80 ℃. The polymerization time is 60-180 min.
In some embodiments, the preparing step comprises:
adding acrylonitrile, graphite or graphite derivatives and a molecular weight regulator into deionized water, and uniformly mixing under the assistance of ultrasound and stirring;
controlling the temperature of a uniformly mixed polymerization system to be 40-80 ℃, dropwise adding the aqueous solution of the initiator to initiate polymerization reaction, wherein the dropwise adding time is 30-60 min, and keeping ultrasonic and stirring treatment in the dropwise adding process;
after the initiator is dripped, the temperature is kept for 30-120 min until the reaction is finished, and ultrasonic treatment and stirring treatment are kept in the polymerization process;
and filtering the product, washing the product with deionized water, and drying the product at 80-100 ℃ to obtain the polyacrylonitrile/graphite composite material.
In another embodiment of the invention, the graphite-doped polyacrylonitrile-based nanocomposite is obtained by the preparation method.
In some embodiments, the molecular weight of polyacrylonitrile in the product is 10000-1000000.
The third embodiment of the invention provides an application of the graphite-doped polyacrylonitrile-based nanocomposite in preparation of carbon fibers or carbon nanofibers.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
Controlling the temperature of a polymerization system at 50 ℃, uniformly mixing 20ml of acrylonitrile (accounting for 10 wt% of the total mass of the solution), 0.02g of flake graphite (accounting for 0.1 wt% of the total monomer content of the flake graphite), and 0.15ml of dodecanethiol, dropwise adding 10ml of mixed initiator aqueous solution consisting of 0.75g of ammonium sulfite and 0.75g of ammonium persulfate within 60min, keeping the temperature for 60min after the dropwise adding is finished, washing the obtained product and drying the product at 95 ℃ under the joint treatment of mechanical stirring and ultrasonic vibration in the whole polymerization process to obtain the final composite material, wherein the step is shown in figure 2.
Example 2
Controlling the temperature of a polymerization system to be 60 ℃, uniformly mixing 20ml of acrylonitrile (accounting for 10 wt% of the total mass of the solution), 0.08g of crystalline flake graphite (accounting for 0.5 wt% of the total monomer content of crystalline flake graphene), 0.15ml of dodecanethiol, dropwise adding 10ml of mixed initiator aqueous solution consisting of 0.5g of ammonium sulfite and 0.5g of ammonium persulfate within 30min, keeping the temperature for 90min after dropwise adding, washing the obtained product and drying the product at 95 ℃ under the joint treatment of mechanical stirring and ultrasonic vibration in the whole polymerization process, thus obtaining the final composite material.
Example 3
Controlling the temperature of a polymerization system to be 70 ℃, uniformly mixing 20ml of acrylonitrile (accounting for 10 wt% of the total mass of the solution), 0.8g of crystalline flake graphite (accounting for 5 wt% of the total monomer content), and 0.15ml of dodecanethiol, dropwise adding 10ml of mixed initiator aqueous solution consisting of 1g of ammonium sulfite and 1g of ammonium persulfate within 60min, preserving heat for 60min after dropwise adding is completed, washing the obtained product with water and drying the product at 95 ℃ under the joint treatment of mechanical stirring and ultrasonic vibration in the whole polymerization process, and obtaining the final composite material, wherein the temperature is shown in figure 1.
Example 4
The polyacrylonitrile/flake graphite composite material obtained in the embodiments 1 to 3 can be prepared into flake graphite doped composite carbon nanofiber through common electrostatic spinning and heat treatment processes, and the example process is as follows:
adding 2g of the polyacrylonitrile/graphite composite material powder into 10ml of dimethyl sulfoxide, heating to 60 ℃, uniformly stirring to obtain a spinning stock solution, pouring the spinning stock solution into a needle tube with the volume of 20ml, assembling an electrostatic spinning needle with the inner diameter of 0.5mm on the needle tube, and carrying out electrostatic spinning, wherein the electrostatic spinning process parameters are as follows: the temperature is 40 ℃, the liquid supply speed is 3ml/h, the electric field intensity is 100kV/m, the moving speed of the sliding table is 10mm/s, the rotating speed of the filament collecting roller is 500rpm, and the nano fiber felt (namely protofilament) is obtained after the solution is completely consumed, namely electrostatic spinning is completed.
The nanofiber mat was cut into a long strip 5cm long and 2cm wide in accordance with the orientation obtained by the take-up roll, and the long strip was stretched to 15cm at 135 ℃ (one end of the long strip was fixed with a clip, and the other end was stretched by a weight) to obtain a nanofiber ribbon.
And pre-oxidizing the hot-drawn nanofiber strip at 280 ℃ for 1h, carbonizing at 1400 ℃ for 5min, and graphitizing at 2800 ℃ for 50s to obtain the final carbon nanofiber.
The carbon nanofibers prepared in example 2 are shown in fig. 3.
And detecting the tensile stress of the prepared three carbon nanofibers. Specifically, the finally obtained carbon nanofiber strip was cut into test bars having a length of 30mm and a width of 1mm, and the test bars were subjected to tensile stress testing by an XQ-1C draft machine manufactured by the university of east hua, and the results are shown in fig. 4, which indicates that the tensile strength of the carbon nanofibers is continuously increased as the amount of graphite added increases.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a graphite-doped polyacrylonitrile-based nano composite material comprises the steps of mixing an acrylonitrile monomer, a carbonaceous material additive, an initiator and a molecular weight regulator and then polymerizing to obtain the graphite-doped polyacrylonitrile-based nano composite material; the method is characterized in that the carbonaceous material additive is graphite, mechanical stirring and ultrasonic treatment are carried out in the polymerization process, and the graphite is crystalline flake graphite or a derivative of the crystalline flake graphite.
2. The method for preparing a graphite-doped polyacrylonitrile-based nanocomposite material as claimed in claim 1, wherein the particle size of the graphite is 0.1 to 100 μm.
3. The method for preparing the graphite-doped polyacrylonitrile-based nanocomposite material as claimed in claim 1, wherein the graphite is added in an amount of 0.1 to 5 wt% based on the mass of acrylonitrile.
4. The method for preparing a graphite-doped polyacrylonitrile-based nanocomposite material as claimed in claim 1, wherein the addition amount of the initiator is 0.01 to 10 wt% of the mass of the acrylonitrile.
5. The method of claim 1, wherein the aqueous precipitation polymerization process is used to prepare the graphite-doped polyacrylonitrile-based nanocomposite.
6. The method for preparing the graphite-doped polyacrylonitrile-based nanocomposite material as claimed in claim 1, wherein the initiator is ammonium persulfate or an ammonium persulfate-ammonium sulfite composite initiation system.
7. The method for preparing a graphite-doped polyacrylonitrile-based nanocomposite material according to claim 1, wherein the polymerization temperature is 40 to 80 ℃ and the polymerization time is 60 to 180 min.
8. A graphite-doped polyacrylonitrile-based nanocomposite material, which is characterized by being obtained by the preparation method of any one of claims 1 to 7.
9. The graphite-doped polyacrylonitrile-based nanocomposite material of claim 8, wherein the molecular weight is 10000 to 1000000.
10. Use of the graphite doped polyacrylonitrile based nanocomposite material of claim 8 or 9 for the preparation of carbon fibers or carbon nanofibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210182895.XA CN114481370A (en) | 2022-02-25 | 2022-02-25 | Graphite-doped polyacrylonitrile-based nano composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210182895.XA CN114481370A (en) | 2022-02-25 | 2022-02-25 | Graphite-doped polyacrylonitrile-based nano composite material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114481370A true CN114481370A (en) | 2022-05-13 |
Family
ID=81483672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210182895.XA Pending CN114481370A (en) | 2022-02-25 | 2022-02-25 | Graphite-doped polyacrylonitrile-based nano composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114481370A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081926A (en) * | 2007-06-26 | 2007-12-05 | 扬州大学 | High conductive polyamide/graphite nano conductive composite material and preparation method thereof |
| CN103545521A (en) * | 2012-07-11 | 2014-01-29 | 长沙永力新能源科技有限公司 | Graphite-based carbon negative composite material in special shell structure and preparation method thereof |
| CN106012110A (en) * | 2016-06-30 | 2016-10-12 | 东华大学 | Flexible carbon fiber and preparation method thereof |
| AU2020103171A4 (en) * | 2020-11-02 | 2021-01-14 | Inner Mongolia Agricultural University | Preparation method and application of graphene/carbon fiber composite material |
| CN113174657A (en) * | 2021-04-07 | 2021-07-27 | 山东大学 | Preparation method and application of graphene-doped carbon fiber |
-
2022
- 2022-02-25 CN CN202210182895.XA patent/CN114481370A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081926A (en) * | 2007-06-26 | 2007-12-05 | 扬州大学 | High conductive polyamide/graphite nano conductive composite material and preparation method thereof |
| CN103545521A (en) * | 2012-07-11 | 2014-01-29 | 长沙永力新能源科技有限公司 | Graphite-based carbon negative composite material in special shell structure and preparation method thereof |
| CN106012110A (en) * | 2016-06-30 | 2016-10-12 | 东华大学 | Flexible carbon fiber and preparation method thereof |
| AU2020103171A4 (en) * | 2020-11-02 | 2021-01-14 | Inner Mongolia Agricultural University | Preparation method and application of graphene/carbon fiber composite material |
| CN113174657A (en) * | 2021-04-07 | 2021-07-27 | 山东大学 | Preparation method and application of graphene-doped carbon fiber |
Non-Patent Citations (1)
| Title |
|---|
| 许晶玮等: "高分子/石墨复合材料的制备与导电性能的研究进展", 《化学通报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101689861B1 (en) | Nanocarbon composite carbon fiber with low cost and high performance and their preparation method | |
| CN102534870B (en) | Preparation method of grapheme-modified acrylonitrile base carbon fiber | |
| Zhou et al. | Development of carbon nanofibers from aligned electrospun polyacrylonitrile nanofiber bundles and characterization of their microstructural, electrical, and mechanical properties | |
| KR101726822B1 (en) | Ultrafine carbon fibers and their preparation method | |
| JP5697258B2 (en) | Method for producing precursor fiber for obtaining high strength and high modulus carbon fiber | |
| CN113913970A (en) | High-performance carbon nanofiber and continuous preparation method thereof | |
| JP5536439B2 (en) | Method for producing precursor fiber for obtaining high strength and high modulus carbon fiber | |
| CN101016659A (en) | Method of preparing Lyocell fiber containing carbon nano tube | |
| JP5251524B2 (en) | Method for producing precursor fiber for obtaining high strength and high modulus carbon fiber | |
| CN113174658A (en) | Preparation method and application of high-regularity doped graphene carbon nanofiber | |
| JP2010185163A (en) | Production method of precursor fiber for obtaining carbon fiber having high strength and high elastic modulus | |
| CN111285949A (en) | Polyacrylonitrile-coated graphene composite material and preparation method and application thereof | |
| Sui et al. | Desirable electrical and mechanical properties of continuous hybrid nano-scale carbon fibers containing highly aligned multi-walled carbon nanotubes | |
| JP2009197365A (en) | Method for producing precursor fiber of carbon fiber, and method for producing the carbon fiber | |
| JP5261367B2 (en) | Method for producing precursor fiber for obtaining high strength and high modulus carbon fiber | |
| CN113235227B (en) | Preparation method and application of composite film | |
| CN111979611B (en) | Lignin/nanocellulose-based carbon fiber and preparation method thereof | |
| CN113174657A (en) | Preparation method and application of graphene-doped carbon fiber | |
| CN110747537B (en) | Preparation method of lignin/graphene-based carbon fiber | |
| WO2011102400A1 (en) | Production method for precursor fibre for obtaining high-strength and high elastic modulus carbon fibre | |
| CN114481370A (en) | Graphite-doped polyacrylonitrile-based nano composite material and preparation method and application thereof | |
| JP4582819B1 (en) | Method for producing high-strength polyacrylonitrile-based carbon fiber | |
| CN114318593B (en) | Fullerene-doped high-regularity carbon nanofiber and preparation method and application thereof | |
| JP2010174161A (en) | Method for producing dispersion of polyacrylonitrile-based polymer for precursor fiber of carbon fiber | |
| CN107747144B (en) | Preparation method for preparing lignin-based hierarchical pore activated carbon fiber based on heat conduction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |