CN106521713A - Preparation method of graphene/mesophase pitch based composite carbon fiber - Google Patents
Preparation method of graphene/mesophase pitch based composite carbon fiber Download PDFInfo
- Publication number
- CN106521713A CN106521713A CN201610990334.7A CN201610990334A CN106521713A CN 106521713 A CN106521713 A CN 106521713A CN 201610990334 A CN201610990334 A CN 201610990334A CN 106521713 A CN106521713 A CN 106521713A
- Authority
- CN
- China
- Prior art keywords
- graphene
- carbon fiber
- mesophase pitch
- add
- 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
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
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a preparation method of graphene/mesophase pitch based composite carbon fiber. Compared with pure mesophase pitch, the graphene/mesophase pitch based composite carbon fiber prepared with the method has unchanged initial heat weight loss temperature, basically identical rheological properties, improved tensile strength and yield strength and basically unchanged conduction performance and modulus.
Description
Technical field
A kind of the present invention relates to fibre manufacturing technology field, more particularly to the compound carbon fiber of Graphene/intermediate phase pitch-based
Preparation method.
Background technology
With the development that science and technology is maked rapid progress, carbon fiber is not only merely used as the reinforcement in composite, goes back quilt
It is widely used in consumer electronic device, skyscraper, integrated circuit, rapid, information engineering, ocean engineering, new energy
The fields such as source, life sciences and national defense construction.Carbon fibe also has good biocompatibility, and people can also as needed to charcoal
The surface functional group of fiber, chemical property, mechanical property and it is adjusted using form so as to be applied to chemical industry, food, biology
The fields such as pharmacy, biological wastewater treatment and fixation of microbe cell, Carbon fiber and carbon fiber composites are the masters of this century new material
One of body.
The presoma for preparing carbon fiber is a lot, can be Colophonium, polyacrylonitrile, polyethylene etc., but up to the present, can be with
Realize only Colophonium, polyimides and the viscose rayon of industrialized production.
Mesophase Pitch-based Carbon Fibers (Mesophase pitch-based carbon fiber, MPCF) are low close because of which
It is many that the excellent properties such as degree, high-moduluss, high heat conductance are widely used in aerospace, automobile, military project, electronic device, biology, the energy etc.
Individual field.But compared with PAN based carbon fibers, the tension and comprcssive strength of Mesophase Pitch-based Carbon Fibers is relatively low, not only makes which
Preparation process becomes difficult, has also had a strong impact on its wider application.So improving Mesophase Pitch-based Carbon Fibers power
The method very Worth Expecting of its conductive performance and modulus is not interfered with while learning performance again.
Focus of the Graphene as Recent study, the thermal conductivity for having fabulous intensity, single-layer graphene are close to theoretical value,
But be also difficult to be used alone at present, used as filler in most cases.
The content of the invention
It is an object of the invention to a kind of preparation method of the compound carbon fiber of Graphene/intermediate phase pitch-based is proposed, to carry
The mechanical property of high mesophase pitch-based carbon fibers, while do not affect its conductive performance and modulus.
It is that, up to this purpose, the present invention is employed the following technical solutions：
A kind of preparation method of the compound carbon fiber of Graphene/intermediate phase pitch-based, including：
(1), under condition of ice bath, under mechanical agitation, crystalline graphite powder is added in 98% concentrated sulphuric acid, add and account for
The sodium nitrate of graphite powder 50-80wt%, and to account for and react 30-120min under the potassium permanganate of 2-4 times of weight of graphite powder, ice bath；
(2) 30-40 DEG C of constant temperature 4-5h is heated to, deionized water and hydrogen peroxide is added, 1-3h is stirred, 5% concentration is added
HCl centrifuge washings are until sulfate radical-free ion, obtains graphene oxide；
(3) graphene oxide is put in the hydrazine hydrate solution of 5-10wt% concentration and is reduced, reduction temperature is 75-90
DEG C, recovery time 0.5-2h obtains Graphene；
(4) mesophase pitch is compared into 100 with the Graphene according to weight:(0.05-1) mix, add ethanol, ultrasound is simultaneously
Stir；
(5) mixture for stirring is heated to into 300-330 DEG C and is incubated 10-60min, then carry out melt spinning,
Obtain composite fibre；
(6) under noble gases or nitrogen protection, composite fibre is raised to into 700 DEG C with the heating rate of 2-4 DEG C/s, subsequently
1000-2000 DEG C is warmed up to 5-6 DEG C of programming rate, room temperature is cooled to, the Graphene/intermediate phase pitch-based is obtained and is combined
Carbon fiber.
The compound carbon fiber of Graphene/intermediate phase pitch-based that method of the present invention is prepared, which is compared to pure
Mesophase pitch, initial thermal weight loss temperature are not changed in, and rheological property is basically identical, and its tensile strength and yield strength are carried
Height, its conductive performance and modulus do not change substantially.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
Embodiment 1
A kind of preparation method of the compound carbon fiber of Graphene/intermediate phase pitch-based, including：
(1), under condition of ice bath, under mechanical agitation, crystalline graphite powder is added in 98% concentrated sulphuric acid, add and account for
The sodium nitrate of graphite powder 50wt%, and to account for and react 30min under the potassium permanganate of 2 times of weight of graphite powder, ice bath；
(2) 30 DEG C of constant temperature 4h are heated to, deionized water and hydrogen peroxide is added, 1h is stirred, the HCl centrifugations of 5% concentration are added
Washing is until sulfate radical-free ion, obtains graphene oxide；
(3) graphene oxide is put in the hydrazine hydrate solution of 10wt% concentration and is reduced, reduction temperature is 75 DEG C, also
Former time 0.5h, obtains Graphene；
(4) mesophase pitch is compared into 100 with the Graphene according to weight:0.05 mixing, adds ethanol, ultrasound simultaneously to stir
Uniformly；
(5) mixture for stirring is heated to into 300 DEG C and is incubated 10min, then carried out melt spinning, be combined
Fiber；
(6) noble gases or nitrogen protection under, composite fibre is raised to into 700 DEG C with the heating rate of 2 DEG C/s, subsequently with
5 DEG C of programming rate is warmed up to 1000 DEG C, is cooled to room temperature, obtains the compound carbon fiber of the Graphene/intermediate phase pitch-based.
Embodiment 2
A kind of preparation method of the compound carbon fiber of Graphene/intermediate phase pitch-based, including：
(1), under condition of ice bath, under mechanical agitation, crystalline graphite powder is added in 98% concentrated sulphuric acid, add and account for
The sodium nitrate of graphite powder 80wt%, and to account for and react 120min under the potassium permanganate of 4 times of weight of graphite powder, ice bath；
(2) 40 DEG C of constant temperature 5h are heated to, deionized water and hydrogen peroxide is added, 3h is stirred, the HCl centrifugations of 5% concentration are added
Washing is until sulfate radical-free ion, obtains graphene oxide；
(3) graphene oxide is put in the hydrazine hydrate solution of 10wt% concentration and is reduced, reduction temperature is 90 DEG C, also
Former time 2h, obtains Graphene；
(4) mesophase pitch is compared into 100 with the Graphene according to weight:1 mixing, adds ethanol, ultrasound simultaneously to stir equal
It is even；
(5) mixture for stirring is heated to into 330 DEG C and is incubated 60min, then carried out melt spinning, be combined
Fiber；
(6) noble gases or nitrogen protection under, composite fibre is raised to into 700 DEG C with the heating rate of 4 DEG C/s, subsequently with
6 DEG C of programming rate is warmed up to 2000 DEG C, is cooled to room temperature, obtains the compound carbon fiber of the Graphene/intermediate phase pitch-based.
Embodiment 3
A kind of preparation method of the compound carbon fiber of Graphene/intermediate phase pitch-based, including：
(1), under condition of ice bath, under mechanical agitation, crystalline graphite powder is added in 98% concentrated sulphuric acid, add and account for
The sodium nitrate of graphite powder 60wt%, and to account for and react 60min under the potassium permanganate of 3 times of weight of graphite powder, ice bath；
(2) 35 DEG C of constant temperature 4h are heated to, deionized water and hydrogen peroxide is added, 2h is stirred, the HCl centrifugations of 5% concentration are added
Washing is until sulfate radical-free ion, obtains graphene oxide；
(3) graphene oxide is put in the hydrazine hydrate solution of 10wt% concentration and is reduced, reduction temperature is 80 DEG C, also
Former time 1h, obtains Graphene；
(4) mesophase pitch is compared into 100 with the Graphene according to weight:0.1 mixing, adds ethanol, ultrasound simultaneously to stir
Uniformly；
(5) mixture for stirring is heated to into 320 DEG C and is incubated 30min, then carried out melt spinning, be combined
Fiber；
(6) noble gases or nitrogen protection under, composite fibre is raised to into 700 DEG C with the heating rate of 3 DEG C/s, subsequently with
5 DEG C of programming rate is warmed up to 1500 DEG C, is cooled to room temperature, obtains the compound carbon fiber of the Graphene/intermediate phase pitch-based.
The compound carbon fiber of Graphene/intermediate phase pitch-based that method described in embodiment 1-3 is prepared, which is compared to pure
Mesophase pitch, initial thermal weight loss temperature is not changed in, and rheological property is basically identical, and its tensile strength and yield strength have
Improve, its conductive performance and modulus do not change substantially.
Claims (1)
1. a kind of Graphene/intermediate phase pitch-based is combined the preparation method of carbon fiber, including：
(1), under condition of ice bath, under mechanical agitation, crystalline graphite powder is added in 98% concentrated sulphuric acid, add and account for graphite
The sodium nitrate of powder 50-80wt%, and to account for and react 30-120min under the potassium permanganate of 2-4 times of weight of graphite powder, ice bath；
(2) be heated to 30-40 DEG C of constant temperature 4-5h, add deionized water and hydrogen peroxide, stir 1-3h, add the HCl of 5% concentration from
Heart washing is until sulfate radical-free ion, obtains graphene oxide；
(3) graphene oxide is put in the hydrazine hydrate solution of 5-10wt% concentration and is reduced, reduction temperature is 75-90 DEG C,
Recovery time 0.5-2h, obtains Graphene；
(4) mesophase pitch is compared into 100 with the Graphene according to weight:(0.05-1) mix, add ethanol, ultrasound simultaneously to stir
Uniformly；
(5) mixture for stirring is heated to into 300-330 DEG C and is incubated 10-60min, then carried out melt spinning, obtain
Composite fibre；
(6) under noble gases or nitrogen protection, composite fibre is raised to into 700 DEG C with the heating rate of 2-4 DEG C/s, subsequently with 5-
6 DEG C of programming rate is warmed up to 1000-2000 DEG C, is cooled to room temperature, obtains the Graphene/intermediate phase pitch-based composite carbon fine
Dimension.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610990334.7A CN106521713A (en) | 2016-11-10 | 2016-11-10 | Preparation method of graphene/mesophase pitch based composite carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610990334.7A CN106521713A (en) | 2016-11-10 | 2016-11-10 | Preparation method of graphene/mesophase pitch based composite carbon fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106521713A true CN106521713A (en) | 2017-03-22 |
Family
ID=58350867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610990334.7A Pending CN106521713A (en) | 2016-11-10 | 2016-11-10 | Preparation method of graphene/mesophase pitch based composite carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106521713A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108624993A (en) * | 2018-05-10 | 2018-10-09 | 湖南大学 | A kind of preparation method without splitting structure high heat conduction mesophase pitch-based carbon fibers |
| CN108794037A (en) * | 2018-06-21 | 2018-11-13 | 西安理工大学 | A kind of preparation method of Carbon foam heat-insulation composite material |
| 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 |
| CN112941668A (en) * | 2021-03-15 | 2021-06-11 | 湖南大学 | Preparation method of mesophase pitch-based graphite fiber with stable structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276477A (en) * | 2013-06-09 | 2013-09-04 | 东莞市比比克电子科技有限公司 | Preparation technology of intermediate phase pitch-based carbon fiber |
| CN103320901A (en) * | 2013-06-01 | 2013-09-25 | 青岛中科昊泰新材料科技有限公司 | Mesophase pitch-based carbon fiber doped with graphene |
| CN104213253A (en) * | 2014-09-15 | 2014-12-17 | 北京化工大学常州先进材料研究院 | Preparation method of novel mesophase pitch-based composite carbon fibers |
| CN105256409A (en) * | 2015-11-17 | 2016-01-20 | 安徽弘昌新材料有限公司 | Mesophase-pitch-based carbon fiber and preparation method thereof |
-
2016
- 2016-11-10 CN CN201610990334.7A patent/CN106521713A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103320901A (en) * | 2013-06-01 | 2013-09-25 | 青岛中科昊泰新材料科技有限公司 | Mesophase pitch-based carbon fiber doped with graphene |
| CN103276477A (en) * | 2013-06-09 | 2013-09-04 | 东莞市比比克电子科技有限公司 | Preparation technology of intermediate phase pitch-based carbon fiber |
| CN104213253A (en) * | 2014-09-15 | 2014-12-17 | 北京化工大学常州先进材料研究院 | Preparation method of novel mesophase pitch-based composite carbon fibers |
| CN105256409A (en) * | 2015-11-17 | 2016-01-20 | 安徽弘昌新材料有限公司 | Mesophase-pitch-based carbon fiber and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 宁淑丽: "《石墨烯/中间相沥青基复合炭纤维的制备及其结构性能研究》", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 屈凌波: "《新型功能材料设计及应用》", 31 May 2014 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108624993A (en) * | 2018-05-10 | 2018-10-09 | 湖南大学 | A kind of preparation method without splitting structure high heat conduction mesophase pitch-based carbon fibers |
| CN108794037A (en) * | 2018-06-21 | 2018-11-13 | 西安理工大学 | A kind of preparation method of Carbon foam heat-insulation composite material |
| 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 |
| CN112941668A (en) * | 2021-03-15 | 2021-06-11 | 湖南大学 | Preparation method of mesophase pitch-based graphite fiber with stable structure |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106521713A (en) | Preparation method of graphene/mesophase pitch based composite carbon fiber | |
| Wu et al. | Large-scale fabrication of flexible EPDM/MXene/PW phase change composites with excellent light-to-thermal conversion efficiency via water-assisted melt blending | |
| CN102560746B (en) | Preparation method of polyacrylonitrile/graphene composite-based carbon fiber | |
| CN102534865B (en) | Ion-enhanced graphene fiber and preparation method thereof | |
| CN104264260B (en) | A kind of graphene/nanometer cellulose composite fiber and preparation method thereof | |
| WO2016138802A1 (en) | Method for preparing biomass graphene by using cellulose as raw material | |
| KR101689861B1 (en) | Nanocarbon composite carbon fiber with low cost and high performance and their preparation method | |
| CN102181961A (en) | Method for preparing graphene functionalized alginate fibers | |
| CN107304490B (en) | Preparation method of graphene/polyimide composite carbon fiber | |
| CN102181153B (en) | Preparation method of carbon nanotube/functionalized carbon fiber reinforced polyimide composite material | |
| CN111074381A (en) | Preparation method of high-strength medium-modulus aviation carbon fiber based on dry jet wet spinning | |
| CN106410181A (en) | Preparation method of graphene composite containing MnO2 nanowires | |
| CN105696312A (en) | Method for modifying carbon fibers by carrying out acidification assisted electrophoretic deposition to initiate graphene oxide deposition | |
| CN109608668A (en) | A kind of preparation of carbon fiber/graphene oxide/epoxy prepreg and carbon fibre composite | |
| CN104862828A (en) | High thermal conductivity carbon fiber and preparation method thereof | |
| CN108193482A (en) | A kind of processing method for carbon fiber surface modification | |
| CN106280273A (en) | A kind of Graphene/epoxy resin composite material and preparation method thereof | |
| CN109422539A (en) | A kind of preparation method of alumina-silica graphene composite ceramics | |
| CN113233453B (en) | High-electric-conductivity heat-conduction graphite material and preparation method thereof | |
| CN106987925B (en) | Functionalized graphene preparation method based on ion exchange | |
| CN112064149A (en) | Method for graphene wet spinning | |
| CN105506785B (en) | A kind of low-density high-strength high-modulus acrylonitrile base carbon fiber and preparation method thereof | |
| CN110846926A (en) | Preparation method of para-nano aramid fiber and carbon nanotube composite paper | |
| CN114291812B (en) | Graphene oxide dispersion liquid, graphene oxide fiber, reduced graphene oxide fiber and preparation method thereof | |
| CN110983494A (en) | Preparation method of aramid-based carbon fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170322 |
|
| RJ01 | Rejection of invention patent application after publication |