CN111979612A - Preparation method of polyacrylonitrile-based carbon nanofibers - Google Patents
Preparation method of polyacrylonitrile-based carbon nanofibers Download PDFInfo
- Publication number
- CN111979612A CN111979612A CN202010861800.8A CN202010861800A CN111979612A CN 111979612 A CN111979612 A CN 111979612A CN 202010861800 A CN202010861800 A CN 202010861800A CN 111979612 A CN111979612 A CN 111979612A
- Authority
- CN
- China
- Prior art keywords
- polyacrylonitrile
- spinning
- fiber
- spinning solution
- nano
- 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.)
- Withdrawn
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
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
- D01D5/0985—Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
Abstract
The invention relates to a preparation method of carbon nanofibers, in particular to a preparation method of polyacrylonitrile-based carbon nanofibers. The process comprises the following steps: dissolving polyacrylonitrile in a solvent to form a spinning solution, supplying the spinning solution to a spinning die head containing a series of spinning holes, and extruding the spinning solution from the spinning holes to form spinning solution trickle; simultaneously, at least one high-speed jet airflow with the temperature of 20-80 ℃ and the speed of 500-3000 times higher than the extrusion speed of the solution trickle is utilized to blow the solution trickle at the jet angle of 0-30 degrees, so that the solution trickle is refined and the solvent is promoted to volatilize to form the polyacrylonitrile nano-fiber; and then placing the polyacrylonitrile nano-fiber in an air atmosphere of 160-300 ℃ for pre-oxidation treatment and a nitrogen atmosphere of 900-1800 ℃ for carbonization treatment to obtain the nano-carbon fiber. The preparation method has the advantages of high production efficiency, simple process, uniform fiber diameter distribution and the like, and is suitable for large-scale production.
Description
Technical Field
The invention relates to a preparation method of carbon nanofibers, in particular to a preparation method of polyacrylonitrile-based carbon nanofibers.
Background
The carbon fiber is a fiber material which is formed by converting an organic fiber material through a series of heat treatments and has the carbon content of more than 90 percent, has a series of excellent performances such as high specific strength, high specific modulus, high temperature resistance, corrosion resistance, fatigue resistance, radiation resistance, electric conduction, heat transfer, shock absorption, noise reduction, small relative density and the like, and belongs to typical high-performance fibers.
The carbon nanofiber is a novel carbon nanomaterial, is a quasi-one-dimensional carbon material between a carbon nanotube and common carbon fiber, has the characteristics of a carbon material, is soft in textile fiber, and has excellent physical and mechanical properties and chemical stability, such as large specific surface area, high mechanical strength and Young modulus, good electrical conductivity, excellent thermal conductivity and thermal stability and the like. With the deep research on the excellent performance of the carbon nanofiber, the application field of the carbon nanofiber is more and more extensive, and the carbon nanofiber can be widely applied to the fields of aerospace, efficient adsorption materials, reinforcing materials, energy environments and the like.
At present, the method for preparing the nano carbon fiber is mainly a vapor phase growth method, such as chinese patent nos. CN 1292984C, CN1172846C and CN 1061706C. The method is easy to generate substances such as carbon black and the like in the production process, further purification is needed, the production cost is high, and the method can only obtain the carbon nanofibers with the length of several micrometers to nearly hundred micrometers, so that the advantages of the carbon nanofibers are difficult to exert. Some recent research papers and patents propose methods for preparing carbon nanofibers by electrospinning, which comprises spinning a precursor of carbon fibers, such as polyacrylonitrile, to obtain polyacrylonitrile nanofibers, and pre-oxidizing and carbonizing the nanofibers to obtain carbon nanofibers. The method can obtain the continuous nano carbon fiber, and the fiber is pure and has certain advantages. However, the current relevant research is mainly based on laboratory equipment research, few large-scale production equipment exist, and the spinning efficiency is low (the spinning speed is generally 0.5-3 mL/h/spinneret orifice).
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problem of providing the method for preparing the polyacrylonitrile nano-fiber by using the solution jet spinning method, and then preparing the nano-carbon fiber by pre-oxidation and carbonization treatment.
A preparation method of polyacrylonitrile-based carbon nanofibers is characterized by comprising the following steps:
(1) preparing a spinning solution: dissolving polyacrylonitrile in a solvent to form a uniform spinning solution with the mass concentration of 6-20%;
the polyacrylonitrile is polyacrylonitrile homopolymer or copolymer, the viscosity average molecular weight is 8-30 ten thousand, wherein the acrylonitrile chain segment accounts for more than 85%, and the rest is methyl acrylate, acrylic acid, acrylamide, itaconic acid or sodium styrene sulfonate;
the solvent is one or a mixture of two or more of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
(2) preparing polyacrylonitrile nano fiber by a solution jet spinning method: supplying the spinning solution to a spinning die head at the speed of 5-30 mL/h/spinning hole, extruding the spinning solution from the spinning hole to form solution trickle, simultaneously blowing the spinning solution trickle at a jet angle of 0-30 degrees with the spinning solution trickle by utilizing at least one high-speed airflow to realize the stretching and thinning of the spinning solution trickle, and simultaneously accelerating the volatilization of the solvent in the spinning solution to form polyacrylonitrile nano fiber with the diameter of 10nm-1 mu m;
the solution jet spinning method is a spinning method for obtaining superfine or even nano fiber by carrying out superfine drawing on extruded fine flow of spinning solution by utilizing high-speed airflow and promoting solvent volatilization, the process steps of the spinning method are 'a preparation method of polymer nano microfiber non-woven fabric' disclosed in Chinese invention patent ZL201110041792.3, the basic principle of the method is that the high-speed airflow is utilized to blow the extruded fine flow of the solution, so that the split of the fine flow of the solution is promoted to generate jet flow, the solvent volatilizes in the jet flow operation process, and the solvent is solidified into fiber;
the temperature of the high-speed jet airflow is 20-80 ℃, and the airflow speed is 500-3000 times higher than the spinning solution fine flow speed.
(3) Pre-oxidation treatment: pre-oxidizing the polyacrylonitrile nano-fiber in an air atmosphere to obtain pre-oxidized nano-fiber, wherein the pre-oxidation temperature is 160-300 ℃, and the pre-oxidation time is 2-3 h;
the pre-oxidation treatment also comprises the step of simultaneously stretching polyacrylonitrile nano-fiber, wherein the stretching multiple is 1.3-5 times;
(4) carbonizing treatment: carbonizing the pre-oxidized nano fiber in a nitrogen atmosphere to obtain the nano carbon fiber, wherein the carbonization temperature is 900-1800 ℃, and the carbonization time is 0.5-3 h.
The diameter of the prepared polyacrylonitrile-based carbon nanofiber is 10nm-1 mu m.
The nano-fiber prepared by the invention is prepared by carrying out preoxidation treatment and carbonization treatment on polyacrylonitrile nano-fiber prepared by solution jet spinning, replaces a gas phase growth method and an electrostatic spinning process, has the advantages of uniform fiber diameter distribution, generally 10nm-1 mu m, typical value of 100nm-500nm, simple process, low energy consumption, short production period, high yield and the like. The prepared nano carbon fiber has the advantages of fine fiber diameter, uniform distribution, good crystallization form and excellent thermal stability, and can be widely applied to the fields of aerospace, high-efficiency adsorption materials, reinforcing materials, energy environments and the like.
Drawings
FIG. 1 is a schematic diagram of a polyacrylonitrile nanofiber preparation apparatus according to an embodiment of the present invention:
in the figure: 1. a spinning solution storage tank; 2. a spinning die head; 21. a spinneret orifice; 22. spinning air gaps; 3. a drying chamber; 4. collecting the net curtain; 5. a pressure controller; 6. a vacuum chamber; 7. an exhaust fan.
FIG. 2 is a scanning electron microscope image of the carbon nanofibers of example 1 of the present invention, which contains the scale of the fiber size, and μm is the length unit μm.
Fig. 3 is a diameter distribution diagram of the carbon fibers in fig. 2.
Detailed Description
The present invention is further illustrated by the following examples.
The invention discloses a preparation method of nano carbon fiber (the preparation method is called as a short method, and is shown in figure 1), which comprises the following process steps: dissolving polyacrylonitrile in a solvent to form a spinning solution, supplying the spinning solution to a spinning die head 2 containing a series of spinning holes through a supply device, and extruding the spinning solution from the spinning holes 21 of the spinning die head 2 to form a spinning solution trickle; simultaneously, at least one high-speed jet air flow enters the spinning die head 2 and blows a thin flow of the extruded spinning solution at a jet angle of 0-30 degrees through an air gap 12 of the spinning die head 2; the high-speed jet airflow realizes the stretching and refining of the spinning solution trickle, and simultaneously accelerates the volatilization of the solvent in the spinning solution to form polyacrylonitrile nano-fiber; placing polyacrylonitrile nano-fiber in an oxidation furnace for pre-oxidation treatment in an oxygen environment, wherein the pre-oxidation temperature is 160-300 ℃, and the pre-oxidation time is 2-3 h; carbonizing the pre-oxidized nano-fiber in a nitrogen atmosphere to obtain the nano-carbon fiber, wherein the carbonization temperature is 900-1800 ℃, the heating rate is 1-15 ℃/min, and the heat preservation treatment time is 0.5-3 h.
The polyacrylonitrile is polyacrylonitrile homopolymer or copolymer, the molecular weight is 8-30 ten thousand, wherein the acrylonitrile chain segment accounts for more than 85%, and the rest is methyl acrylate, acrylic acid, acrylamide, itaconic acid or sodium styrene sulfonate.
The solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide, and when a multi-solvent blending system is adopted, the mixing ratio of various solvents is not limited.
The temperature of the high-speed jet airflow is 20-80 ℃, the jet speed of the high-speed jet airflow is 3000 times higher than the extrusion speed of the spinning solution trickle, and the jet included angle between the high-speed jet airflow and the spinning solution trickle is 0-30 degrees.
In order to improve the mechanical property of the nano carbon fiber, the invention is further characterized in that the polyacrylonitrile nano fiber is stretched in the pre-oxidation treatment process, and the stretching multiple is 1.3-5 times.
Nothing in this specification is said to apply to the prior art.
Specific examples of the present invention are given below, but the scope of protection of the claims of the present invention is not limited to the specific examples.
Example 1.
(1) Preparing a spinning solution: dissolving polyacrylonitrile with the viscosity-average molecular weight of 9 ten thousand into N, N-dimethylformamide according to the mass fraction of 12%, and stirring until the polyacrylonitrile is uniformly mixed to prepare a spinning solution;
(2) preparing polyacrylonitrile nano fiber by a solution jet spinning method: supplying the spinning solution to the spinning die head 2 through a metering pump at the speed of 12 mL/h/spinneret orifice, and extruding the spinning solution from the spinneret orifice 21 of the spinning die head 2 to form a spinning solution trickle; simultaneously, two high-speed jet air flows with the temperature of 40 ℃ are blown to the extruded spinning solution trickle through the air gap 12 at the jet angle of 30 degrees, the air flow speed is controlled to be 800 times of the extrusion speed of the solution trickle, and the high-speed air flows stretch the solution trickle and promote the solvent to volatilize so as to form the polyacrylonitrile nano-fiber;
(3) pre-oxidation treatment: placing the prepared polyacrylonitrile nano-fiber in a pre-oxidation furnace, and treating for 2h at 190 ℃ to obtain pre-oxidized fiber;
(4) carbonizing treatment: carbonizing the pre-oxidized fiber in a nitrogen atmosphere to obtain the carbon nanofiber, wherein the carbonization temperature is 1000 ℃, the heating rate is 8 ℃/min, and the heat preservation treatment time is 2h to obtain the carbon nanofiber.
The scanning electron microscope of the prepared nano carbon fiber is shown in figure 2, the diameter distribution diagram is shown in figure 3, the diameter distribution is mainly 100-340nm, and the average diameter is 170 nm.
Example 2.
(1) Preparing a spinning solution: dissolving polyacrylonitrile with the viscosity-average molecular weight of 12 ten thousand into N, N-dimethylacetamide according to the mass fraction of 10%, and stirring until the polyacrylonitrile and the N, N-dimethylacetamide are uniformly mixed to prepare a spinning solution;
(2) preparing polyacrylonitrile nano fiber by a solution jet spinning method: supplying the spinning solution to the spinning die head 2 through a metering pump at the speed of 22 mL/h/spinneret orifice, and extruding the spinning solution from the spinneret orifice 21 of the spinning die head 2 to form a spinning solution trickle; simultaneously, two high-speed jet air flows with the temperature of 50 ℃ are blown to the extruded spinning solution trickle through an air gap 12 at the jet angle of 15 degrees, the air flow speed is controlled to be 1200 times of the extrusion speed of the solution trickle, and the high-speed air flows stretch the solution trickle and promote the solvent to volatilize so as to form the polyacrylonitrile nano-fiber;
(3) pre-oxidation treatment: placing the prepared polyacrylonitrile nano-fiber in a pre-oxidation furnace, and treating for 3h at 200 ℃ to obtain pre-oxidized fiber;
(4) carbonizing treatment: carbonizing the pre-oxidized fiber in a nitrogen atmosphere to obtain the carbon nanofiber, wherein the carbonization temperature is 1100 ℃, the heating rate is 10 ℃/min, and the heat preservation treatment time is 2h to obtain the carbon nanofiber.
Example 3.
(1) Preparing a spinning solution: dissolving polyacrylonitrile with the viscosity-average molecular weight of 28 ten thousand into N, N-dimethylacetamide/dimethyl sulfoxide (1:1, v/v) according to the mass fraction of 8%, and stirring until the polyacrylonitrile is uniformly mixed to prepare a spinning solution;
(2) preparing polyacrylonitrile nano fiber by a solution jet spinning method: supplying the spinning solution to the spinning die head 2 through a metering pump at the rate of 30 mL/h/spinneret orifice, and extruding the spinning solution from the spinneret orifice 21 of the spinning die head 2 to form a spinning solution trickle; simultaneously, two high-speed jet air flows with the temperature of 50 ℃ are blown to the extruded spinning solution trickle through an air gap 12 at the jet angle of 8 degrees, the air flow speed is controlled to be 2200 times of the extrusion speed of the solution trickle, and the high-speed air flows stretch the solution trickle and promote the solvent to volatilize so as to form the polyacrylonitrile nano-fiber;
(3) pre-oxidation treatment: placing the prepared polyacrylonitrile nano-fiber in a pre-oxidation furnace, carrying out tension drafting with the drafting multiple being 2.5 times, and treating at 220 ℃ for 3 hours to obtain pre-oxidized fiber;
(4) carbonizing treatment: carbonizing the pre-oxidized fiber in a nitrogen atmosphere to obtain the carbon nanofiber, wherein the carbonization temperature is 1800 ℃, the heating rate is 10 ℃/min, and the heat preservation treatment time is 3h to obtain the carbon nanofiber.
Claims (5)
1. A preparation method of polyacrylonitrile-based carbon nanofibers is characterized by comprising the following steps:
(1) preparing a spinning solution: dissolving polyacrylonitrile in a solvent to form a uniform spinning solution with the mass concentration of 6-20%;
(2) preparing polyacrylonitrile nano fiber by a solution jet spinning method: supplying the spinning solution to a spinning die head at the speed of 5-30 mL/h/spinning hole, extruding the spinning solution from the spinning hole to form solution trickle, simultaneously blowing the spinning solution trickle at a jet angle of 0-30 degrees with the spinning solution trickle by utilizing at least one high-speed airflow to realize the stretching and thinning of the spinning solution trickle, and simultaneously accelerating the volatilization of the solvent in the spinning solution to form polyacrylonitrile nano fiber with the diameter of 10nm-1 mu m;
(3) pre-oxidation treatment: pre-oxidizing the polyacrylonitrile nano-fiber in an air atmosphere to obtain pre-oxidized nano-fiber, wherein the pre-oxidation temperature is 160-300 ℃, and the pre-oxidation time is 2-3 h;
(4) carbonizing treatment: carbonizing the pre-oxidized nano fiber in a nitrogen atmosphere to obtain the nano carbon fiber, wherein the carbonization temperature is 900-1800 ℃, and the carbonization time is 0.5-3 h.
2. The method for preparing polyacrylonitrile-based filamentous nanocarbon according to claim 1, wherein the polyacrylonitrile in the step (1) is polyacrylonitrile homopolymer or copolymer, the viscosity-average molecular weight is 8 to 30 ten thousand, wherein the acrylonitrile segment accounts for more than 85%, and the rest is methyl acrylate, acrylic acid, acrylamide, itaconic acid or sodium styrene sulfonate.
3. The method for preparing polyacrylonitrile-based filamentous nanocarbon according to claim 1, wherein the solvent in the step (1) is one or a mixture of two or more of N, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide.
4. The method for preparing polyacrylonitrile-based filamentous nanocarbon according to claim 1, wherein the temperature of the high-speed jet air flow in the step (2) is 20-80 ℃, and the air flow velocity is higher than the fine flow velocity of the spinning solution by 500-3000 times.
5. The method for preparing polyacrylonitrile-based filamentous nanocarbon according to claim 1, wherein the pre-oxidation treatment further comprises simultaneously stretching polyacrylonitrile nanofibers at a stretch ratio of 1.3 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010861800.8A CN111979612A (en) | 2020-08-25 | 2020-08-25 | Preparation method of polyacrylonitrile-based carbon nanofibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010861800.8A CN111979612A (en) | 2020-08-25 | 2020-08-25 | Preparation method of polyacrylonitrile-based carbon nanofibers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111979612A true CN111979612A (en) | 2020-11-24 |
Family
ID=73442700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010861800.8A Withdrawn CN111979612A (en) | 2020-08-25 | 2020-08-25 | Preparation method of polyacrylonitrile-based carbon nanofibers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111979612A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102121173A (en) * | 2011-02-22 | 2011-07-13 | 天津工业大学 | Method for preparing sound-absorbing and heat-insulating materials formed by superfine fiber nonwovens |
| CN102936764A (en) * | 2012-11-27 | 2013-02-20 | 天津工业大学 | Preparation method of polyacrylonitrile-based carbon nanofibers |
-
2020
- 2020-08-25 CN CN202010861800.8A patent/CN111979612A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102121173A (en) * | 2011-02-22 | 2011-07-13 | 天津工业大学 | Method for preparing sound-absorbing and heat-insulating materials formed by superfine fiber nonwovens |
| CN102936764A (en) * | 2012-11-27 | 2013-02-20 | 天津工业大学 | Preparation method of polyacrylonitrile-based carbon nanofibers |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102936764A (en) | Preparation method of polyacrylonitrile-based carbon nanofibers | |
| CN102534870B (en) | Preparation method of grapheme-modified acrylonitrile base carbon fiber | |
| CN106930004B (en) | The method that electrostatic spinning prepares flexible silicon carbide/carbon nanotube composite cellulosic membrane | |
| CN101112980A (en) | Method for preparing nano carbon fibre by using polyacryl-nitrile (PAN) | |
| CN110079896B (en) | Silicon carbide nanofiber bundle and preparation method thereof | |
| CN105696114B (en) | Controllable carbon fibre material aperture and the preparation method and carbon fibre material of porosity | |
| CN113913970A (en) | High-performance carbon nanofiber and continuous preparation method thereof | |
| CN109023590B (en) | Silicon carbide hollow fiber and preparation method thereof | |
| CN101250770A (en) | Method for manufacturing polyacrylonitrile-based carbon fiber with enganced carbon nano-tube | |
| CN106567157B (en) | Preparation method of graphene nanoribbon in-situ toughening carbon nanofibers | |
| CN104649260A (en) | Preparation method of graphene nano fibers or nanotubes | |
| CN105734724A (en) | Novel method for preparing carbon nanofibers through electrospinning | |
| CN113174658A (en) | Preparation method and application of high-regularity doped graphene carbon nanofiber | |
| CN102912476A (en) | Preparation method of carbonized silicon (SiC) sub-micron fibers | |
| CN110499550B (en) | Centrifugal spinning preparation method of polyacrylonitrile-based pre-oxidized fiber and carbon fiber | |
| CN106854779A (en) | A kind of carbon nano-tube oriented enhanced carbon fibre composite and preparation method thereof | |
| Liu et al. | Effect of spinning conditions on the mechanical properties of PA6/MWNTs nanofiber filaments | |
| Rafique et al. | Fabrication of ultra thin and aligned carbon nanofibres from electrospun polyacrylonitrile nanofibres | |
| CN113174657A (en) | Preparation method and application of graphene-doped carbon fiber | |
| CN111979612A (en) | Preparation method of polyacrylonitrile-based carbon nanofibers | |
| CN101250769B (en) | Method for manufacturing electric spinning of high-powered carbon nano-tube/PBO composite fiber | |
| CN108842223A (en) | A kind of preparation method of polyvinylidene fluoride nanometer fabric nonwoven cloth | |
| WO2011102400A1 (en) | Production method for precursor fibre for obtaining high-strength and high elastic modulus carbon fibre | |
| CN107217334B (en) | Carbon nano-fiber and preparation method thereof and device | |
| CN110983491A (en) | Method for manufacturing high-thermal-conductivity mesophase pitch-based carbon fibers at low temperature |
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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20201124 |