CN109371506A - A kind of preparation method of graphene composite fibre - Google Patents
A kind of preparation method of graphene composite fibre Download PDFInfo
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- CN109371506A CN109371506A CN201811273377.9A CN201811273377A CN109371506A CN 109371506 A CN109371506 A CN 109371506A CN 201811273377 A CN201811273377 A CN 201811273377A CN 109371506 A CN109371506 A CN 109371506A
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- fiber
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- 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
- D01F9/225—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 from stabilised polyacrylonitriles
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- 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
Abstract
The present invention provides a kind of preparation methods of graphene composite fibre, prepare including mixed solution: preparing the mixed solution of graphene, polymer and solvent according to the proportion；Fiber solidifying spinneret: the mixing cured rear spinneret of mixed solution and solidification liquid is generated by fiber using spinning head；Dopamine modification: the fiber prepared in upper step is immersed in the aqueous dopamine solution that pH is 8.5 and is maintained at 60 DEG C；It is introduced into polybenzazole amine: the fiber surface polymerization polybenzazole amine obtained in step S300；Carbonization annealing heat-treatment: the fiber after drying is carbonized 1h at a temperature of 2800 DEG C~3200 DEG C, then anneal under the conditions of 750 DEG C~850 DEG C 1h, the present invention is by introducing polybenzazole amine, adjusting the proportion between polymer and graphene and taking carbonization annealing process, so that the structure of graphene composite fibre is more compact, the mechanical strength and thermal stability of graphene composite fibre are greatly improved.
Description
Technical field
The present invention relates to field of compound material more particularly to a kind of preparation methods of graphene composite fibre.
Background technique
Graphene is a kind of Two-dimensional Carbon nanometer material for forming hexangle type in honeycomb lattice with sp2 hybridized orbit by carbon atom
Material.Graphene has excellent optics, electricity, mechanical characteristic, passes in materialogy, micro-nano technology, the energy, biomedicine and drug
Pass etc. is with important application prospects, it is considered to be a kind of future revolutionary material.The common power production of graphene
Method be mechanical stripping method, oxidation-reduction method, SiC epitaxial growth method, film production method is chemical vapour deposition technique.
It increases sharply since population increases with industrial development and Fresh fats, the demand to fiber
Demand is continuously increased.Since E.I.Du Pont Company in 1938 announces to release a kind of novel synthetic fibers of entitled nylon,
Develop polyester fiber, acrylic fibers peacekeeping polyurethane fiber.In recent years, the high-performance and superelevation using new material are being developed
Functional fibre and nanofiber, in these carbon-based composite fibres, it is non-resilient to provide to add various reinforcing materials, non-resilient
, it is better than other kinds of fiber, can be made into lightweight, high-intensitive, elastomeric composite material.
Particularly, for graphene tool there are six the structure that hexagonal carbon connects to each other to form two-dimension single layer, graphene is one
Kind can pass through the material that a kind of material of first separation graphite obtains.Simplest method is removed with adhesive tape.This
Outside, it is available.Graphene has high conductivity (1 x 10-6 Ω cm), electrical property, such as high electron mobility, (2650 m
2/g), high resiliency (1 TPa), chemical safety.
However polymer is introduced into graphene fiber or graphene, there are mechanical strengths for the graphene fiber produced
Low disadvantage is easy to produce abrasion in actual use, even fractures, and limit graphene composite fibre applies model
It encloses, haves the defects that certain.
Summary of the invention
In view of the above-mentioned problems, the present invention proposes that a kind of preparation method of graphene composite fibre, the present invention are poly- by introducing
Indoles amine adjusts the proportion between polymer and graphene and takes carbonization annealing process, so that graphene composite fibre
Structure is more compact, greatly improves the mechanical strength and thermal stability of graphene composite fibre, can efficiently solve background
The problem of technology proposes.
In order to solve the problem above-mentioned, the present invention proposes a kind of preparation method of graphene composite fibre, including walks as follows
It is rapid:
S100, mixed solution preparation: the mixed solution of graphene, polymer and solvent is prepared according to the proportion；
S200, fiber solidifying spinneret: the mixing cured rear spinneret of mixed solution and solidification liquid is generated by fiber using spinning head；
S300, dopamine modification: the fiber prepared in step S200 is immersed in the aqueous dopamine solution that pH is 8.5 and is protected
It holds at 60 DEG C；
S400, it is introduced into polybenzazole amine: the fiber surface polymerization polybenzazole amine obtained in step S300；
S500, carbonization annealing heat-treatment: the fiber after drying is carbonized 1h at a temperature of 2800 DEG C~3200 DEG C, then 750
DEG C~850 DEG C under the conditions of anneal 1h.
Further improvement lies in that: the step of in step S100 prepared by mixed solution includes:
S101, the liquid crystal graphene being dispersed in water simultaneously remove moisture therein；
S102, above-mentioned same amount of dimethylformamide, preparation dispersion solution is added；
S103, polymer is added into dispersion solution and mixes, mixed solution is prepared, so that the weight ratio of graphene and polymer
For 80wt%:20wt%.
Further improvement lies in that: the polymer in step S100 is polyacrylonitrile, and the molecular weight of polyacrylonitrile is
150000~300000.
Further improvement lies in that: solidification liquid is specially the mixture of water and isopropanol that weight ratio is 7:3 in step S200.
Further improvement lies in that: the injection rate of spinning head is 5ml/hr in step S200, and the rotation speed of spinning head is
30rpm。
Further improvement lies in that: in step S400 before introducing polybenzazole amine, cleaning is carried out to fiber and at 60 DEG C
Dry 30min in inert gas environment.
Further improvement lies in that: the carbonization annealing process of fiber carries out in nitrogen environment in step S500.
The invention has the benefit that
(1) present invention is by having carried out carbonization treatment to the fiber of preparation, so that being released in polymer and graphene containing carbon
It is put into the outside of graphene composite fibre, the polymer after carbonization has hexagonal honeycomb structure identical with carbon and nitrogen, into one
Step improves the effect of the high-strength characteristic of graphene composite fibre；
(2) present invention is by introducing polybenzazole amine, adjusting the proportion between polymer and graphene and taking carbonization lehr attendant
Skill greatly improves the mechanical strength and heat of graphene composite fibre so that the structure of graphene composite fibre is more compact
Stability improves the preparation quality that graphene meets fiber.
Detailed description of the invention
Fig. 1 is graphene composite fibre preparation method flow chart of the present invention.
Fig. 2 is one experimental result picture of EXPERIMENTAL EXAMPLE of the present invention.
Fig. 3 is the SEM photograph of graphene composite fiber surface in present invention preparation comparative example two.
Fig. 4 is the SEM photograph on graphene composite fibre amplification surface in present invention preparation comparative example two.
Fig. 5 is the SEM photograph of graphene composite fiber surface in present invention preparation embodiment one.
Fig. 6 is the SEM photograph on graphene composite fibre amplification surface in present invention preparation embodiment one.
Fig. 7 is the thermal gravimetric analysis results figure of graphene composite fibre in present invention preparation comparative example two.
Fig. 8 is the thermal gravimetric analysis results figure of graphene composite fibre in present invention preparation embodiment one.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention is further described below in conjunction with embodiment, the present embodiment
For explaining only the invention, it is not intended to limit the scope of the present invention..
Prepare embodiment one:
According to Fig. 1,2,3,4,5,6,7,8, the present embodiment proposes a kind of preparation method of graphene composite fibre, including
Following steps:
S100, mixed solution preparation: the mixed solution of graphene, polymer and solvent is prepared according to the proportion；
S200, fiber solidifying spinneret: the mixing cured rear spinneret of mixed solution and solidification liquid is generated by fiber using spinning head；
S300, dopamine modification: the fiber prepared in step S200 is immersed in the aqueous dopamine solution that pH is 8.5 and is protected
It holds at 60 DEG C；
S400, fiber are cleaned and dried: the fiber for immersing dopamine solution being washed with clear water, and the dry 30min at 60 DEG C；
S500, carbonization annealing heat-treatment: the fiber after drying is carbonized 1h at a temperature of 2800 DEG C~3200 DEG C, then 750
DEG C~850 DEG C under the conditions of anneal 1h.
In the present embodiment, the step of mixed solution preparation, includes: in step S100
S101, the liquid crystal graphene being dispersed in water simultaneously remove moisture therein；
S102, above-mentioned same amount of dimethylformamide, preparation dispersion solution is added；
S103, polymer is added into dispersion solution and mixes, mixed solution is prepared, so that the weight ratio of graphene and polymer
For 80wt%:20wt%.
In the present embodiment, polymer in step S100 is polyacrylonitrile, and the molecular weight of polyacrylonitrile be 150000~
300000, polyacrylonitrile is used for fibre spinning.
In the present embodiment, solidification liquid is specially the mixture of water and isopropanol that weight ratio is 7:3, solidification in step S200
The addition of liquid forms graphene composite fibre so that graphene, polyacrylonitrile combine stronger.
In the present embodiment, the injection rate of spinning head is 5ml/hr in step S200, and the rotation speed of spinning head is
30rpm。
In the present embodiment, in step S400 before introducing polybenzazole amine, cleaning is carried out to fiber and in 60 DEG C of inertia
Dry 30min in gaseous environment, removes the dopamine solution on fiber, avoid dopamine solution occur polymerization in fiber surface and
Influence the quality of fiber.
In the present embodiment, the carbonization annealing process of fiber carries out in nitrogen environment in step S500, and be carbonized annealing process
It carries out under high temperature environment, the addition of nitrogen, it is therefore prevented that fiber aoxidizes under the high temperature conditions, plays certain protection
Effect.
In order to protrude the method for the present invention substantive features and significant progress, the present invention also provides preparation comparative examples
Two, it prepares comparative example three and EXPERIMENTAL EXAMPLE carries out performance comparison.
Prepare comparative example two:
The fiber obtained in embodiment step S200 is skipped into step S300 and prepares graphene composite fibre.
EXPERIMENTAL EXAMPLE one:
According to graphene content measurement mechanical performance in graphene composite fibre, experimental method be using the embodiment of the present invention,
Only change the weight ratio of graphene and polymer, the mass ratio of graphene and polymer in mixed solution is respectively 10wt%:
90wt%, 20wt%:80wt%, 30wt%:70wt%, 40wt%:60wt%, 50wt%:50wt%, 60wt%:40wt%, 70wt%:
30wt%, every kind of mixed solution is used as experimental group and is answered with forming respective graphene by 8 0wt%:20wt%, 90wt%:10wt%
Condensating fiber measures respectively and compares intensity and modulus.
EXPERIMENTAL EXAMPLE two:
Whether the thermal stability measurement of the graphene composite fibre containing polybenzazole amine coating is compared, and experimental method is according to this hair
Two kinds of compound fibres of graphene with or without polybenzazole amine coating in bright preparation embodiment one and preparation comparative example one
Dimension carries out thermogravimetric analysis according to heat treatment of two kinds of graphene composite fibres in 100 DEG C to 1000 DEG C temperature ranges.
Comparative analysis result are as follows:
(1) compound according to the graphene in Fig. 3, Fig. 4, Fig. 5 and Fig. 6 preparation embodiment one shown and preparation comparative example two
The surface of fiber and the SEM figure of cross section, in preparation embodiment one, i.e., the graphene composite fibre coated with polybenzazole amine is horizontal
Cross-sectional internal has the structure of relative compact, shows the effect for improving composite fibre intensity.
(2) experimental result picture of the EXPERIMENTAL EXAMPLE one shown according to fig. 2, when in mixed solution graphene content with polymerize
Object content ratio be 80wt%:20wt% when, the graphene composite fibre have 220MPa highest tensile strength, show graphene and
The range effects fibre strength of polymer weight ratio.
(3) the thermal gravimetric analysis results figure shown according to Fig. 7 and Fig. 8, in the graphene composite fibre undoped with polybenzazole amine
Weight is reduced rapidly after 200 DEG C, and total weight loss is up to 25% at 400 DEG C, and doped with the compound fibre of the graphene of polybenzazole amine
Dimension, even if being kept for 1000 degrees Celsius in temperature, loss width is also little, the introducing of polybenzazole amine, and it is multiple to greatly improve graphene
The thermal stability of condensating fiber.
The basic principles, main features and advantages of the invention have been shown and described above.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes and improvements
It all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended claims and its equivalent circle
It is fixed.
Claims (7)
1. a kind of preparation method of graphene composite fibre, which comprises the steps of:
S100, mixed solution preparation: the mixed solution of graphene, polymer and solvent is prepared according to the proportion；
S200, fiber solidifying spinneret: the mixing cured rear spinneret of mixed solution and solidification liquid is generated by fiber using spinning head；
S300, dopamine modification: the fiber prepared in step S200 is immersed in the aqueous dopamine solution that pH is 8.5 and is protected
It holds at 60 DEG C；
S400, it is introduced into polybenzazole ammonia: the fiber surface polymerization polybenzazole amine obtained in step S300；
S500, carbonization annealing heat-treatment: the fiber after drying is carbonized 1h at a temperature of 2800 DEG C~3200 DEG C, then 750
DEG C~850 DEG C under the conditions of anneal 1h.
2. a kind of preparation method of graphene composite fibre according to claim 1, which is characterized in that mixed in step S100
Closing the step of prepared by solution includes:
S101, the liquid crystal graphene being dispersed in water simultaneously remove moisture therein；
S102, above-mentioned same amount of dimethylformamide, preparation dispersion solution is added；
S103, polymer is added into dispersion solution and mixes, mixed solution is prepared, so that the weight ratio of graphene and polymer
For 80wt%:20wt%.
3. a kind of preparation method of graphene composite fibre according to claim 1, it is characterised in that: in step S100
Polymer is polyacrylonitrile, and the molecular weight of polyacrylonitrile is 150000~300000.
4. a kind of preparation method of graphene composite fibre according to claim 1, it is characterised in that: coagulated in step S200
Solid-liquid is specially the mixture of the water that weight ratio is 7:3 and isopropanol.
5. a kind of preparation method of graphene composite fibre according to claim 1, it is characterised in that: sprayed in step S200
The injection rate of silk head is 5ml/hr, and the rotation speed of spinning head is 30rpm.
6. a kind of preparation method of graphene composite fibre according to claim 1, it is characterised in that: in step S400
It introduces before polybenzazole amine, cleaning and the dry 30min in 60 DEG C of inert gas environment is carried out to fiber.
7. a kind of preparation method of graphene composite fibre according to claim 2, it is characterised in that: fine in step S500
The carbonization annealing process of dimension carries out in nitrogen environment.
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Cited By (2)
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| CN110217011A (en) * | 2019-05-30 | 2019-09-10 | 韦俊刚 | A kind of preparation method of the anti-aging fountain solution of salt tolerant |
| CN113355762A (en) * | 2021-05-27 | 2021-09-07 | 上海茂腾针织有限公司 | High-strength acetate fiber and preparation method thereof |
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Application publication date: 20190222 |