CN112481733A - Graphene polymer composite membrane, modified resin-based composite material thereof and preparation method - Google Patents
Graphene polymer composite membrane, modified resin-based composite material thereof and preparation method Download PDFInfo
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
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- 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
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- 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
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/14—Mixture of at least two fibres made of different materials
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
Abstract
The invention relates to a graphene polymer composite film, a modified resin-based composite material thereof and a preparation method, and belongs to the field of high-performance composite materials. The invention provides a graphene polymer composite membrane and a modified resin-based composite material thereof, which are composed of a graphene material, a thermoplastic polymer and a resin-based composite material, wherein the graphene material and the thermoplastic polymer exist between layers of the resin-based composite material in the form of a graphene thermoplastic polymer composite membrane with a micro porous structure. The invention provides a preparation method of a graphene polymer composite membrane modified resin matrix composite material, which is used for preparing a graphene polymer composite membrane from a graphene material and a thermoplastic polymer and further preparing the modified resin matrix composite material. The porous structure of the graphene polymer composite film is beneficial to mutual combination with resin in the forming process, improves the interlayer uniformity and heat resistance of the composite material, effectively improves the mechanical property of the composite material, and has higher practical application value.
Description
Technical Field
The invention relates to a modified high-performance composite material and a preparation method thereof, in particular to a graphene/polymer composite film, a modified resin-based composite material and a preparation method thereof.
Background
The method effectively improves the impact damage resistance of the resin matrix composite, namely realizes high toughening of the composite, and is a main research direction of high-performance composite. The existing toughening composite material method mainly uses 1) rubber, 2) thermoplastic polymer, 3) rigid particles and resin matrix to be blended and introduced into the composite material, so as to achieve the toughening effect. Currently, there is another method of interlaminar toughening, namely laying down thermoplastic polymer powder between the layers of a composite material,A dense structure of thermoplastic polymer film or carbon nanotube film to improve toughness. Although the thermoplastic polymer film and the carbon nanotube film laid among the layers can effectively improve the impact damage resistance of the composite material, the compact structure of the film seriously hinders the flow of the matrix resin among the layers and the discharge of volatile components among the layers, thereby causing the quality reduction of the composite material. In addition, the application of the carbon nanotube film in composite materials is limited by the difficulty and discontinuity of the preparation process of the carbon nanotube film, the small size of the film and the like. In addition, inventions cn201410545346.x, CN201210217642.8, cn200710063099.x propose a method for directly attaching a thermoplastic polymer toughening agent or a carbon nanotube toughening agent to the surface of a fiber preform or a prepreg by adding a step of electrospinning and then obtaining a toughened composite material. The proposed method requires improvements in the production steps and equipment of the fiber preform and prepreg, and is not easy to popularize and utilize. Compared with the carbon nano tube, the graphene has good elasticity and extremely large specific surface area (the specific surface area is 2630 m)2g-1) Extremely high Young's modulus (about 1TPa) and breaking strength (130GPa), and is suitable for developing light-weight high-performance composite materials. The graphene is used as a reinforcing and toughening material and is added into the composite material together with the thermoplastic polymer, so that the strength and toughness of the composite material can be further improved, and therefore the invention provides a light high-performance composite material simultaneously containing the graphene and the thermoplastic polymer and a preparation method of the high-performance composite material directly oriented to production.
Disclosure of Invention
The invention provides a composite film material of graphene and a thermoplastic polymer and a resin matrix composite material synergistically modified by the composite film material, and also provides a preparation method of the composite film material of graphene and the thermoplastic polymer and the resin matrix composite material synergistically modified by the composite film material.
The technical scheme of the invention is as follows: a graphene polymer composite film modified resin matrix composite material comprises (a) a graphene material, (b) a thermoplastic polymer and (c) a resin matrix composite material, wherein the graphene material and the thermoplastic polymer exist between resin matrix composite material layers in the form of a graphene polymer composite film; the graphene polymer composite membrane is a fibrous porous structure formed by a graphene material and a thermoplastic polymer, and the resin matrix composite material is dissolved in the porous structure and combined into a whole in the forming process; wherein the mass ratio of the graphene material to the thermoplastic polymer is 1: 1-50; more preferably 1: 5-40; more preferably 1: 10-20, so that the mechanical property of the composite material is further improved by improving the graphene content under the condition of meeting the preparation process requirement of the polymer composite film.
The diameter of the graphene polymer composite membrane fiber is 200-2000 nm, so that the graphene polymer composite membrane fiber is fully ensured to have a higher specific surface area, and interface contact and binding force between the graphene polymer composite membrane fiber and resin are increased.
The thickness of the graphene polymer composite film is 5-50 mu m, so that the graphene polymer composite film fiber porous structure has enough space to be fully combined with resin, and the interface integrity and the mechanical property of the composite material are ensured.
The graphene material and the thermoplastic polymer are fully mixed, so that graphene and the polymer in the graphene thermoplastic polymer fiber are uniformly distributed, the process is relatively simple, the cost is low, and the uniform dispersion of the graphene in a composite material interface is facilitated.
The graphene material is attached to the surface of the thermoplastic polymer fiber, so that the surface of the thermoplastic polymer fiber has a raised or wrinkled structure, the interface bonding area between the fiber and the resin can be further increased, and the interface bonding strength of the composite material is improved.
The graphene material in the graphene polymer composite film modified resin-based composite material is one or a combination of single-layer graphene, double-layer graphene oxide, reduced graphene oxide and functionalized graphene, and is selected from 3-10 layers of graphene, graphene oxide, reduced graphene oxide and functionalized graphene.
The thermoplastic polymer in the graphene polymer composite membrane modified resin matrix composite material is polyether ketone, polyether ether ketone, polyether imide, polysulfone, polyether sulfone, phenolphthalein modified polyether sulfone, polyphenylene sulfide, polyphenylene oxide or polyamide.
The resin-based composite material in the graphene polymer composite film modified resin-based composite material comprises an epoxy resin-based composite material, a cyanate resin-based composite material, a bismaleimide resin-based composite material and a polyimide resin-based composite material, and the epoxy resin-based composite material is preferably selected.
A graphene polymer composite film is prepared from a graphene polymer composite film and a graphene oxide composite film, wherein the graphene polymer composite film is prepared from a graphene oxide composite film and a graphene oxide composite film, and the graphene oxide composite film comprises the following components in a mass ratio of 1: the 1-50 graphene material forms a fibrous porous structure by fusing or attaching on thermoplastic polymer fibers, wherein the fibrous diameter is 100-2000 nm.
A preparation method of a graphene polymer modified resin matrix composite material comprises the steps of firstly preparing a graphene material, a thermoplastic polymer and a solvent into a mixed solution of graphene and the thermoplastic polymer or respectively preparing the graphene material and the thermoplastic polymer into solutions, then carrying out spinning to form a graphene polymer composite film, then placing the graphene polymer composite film between resin matrix composite material layers, and obtaining the graphene polymer modified resin matrix composite material through a corresponding composite material forming method.
According to the preparation method of the graphene polymer modified resin matrix composite material, the preparation process of the graphene polymer composite film is as follows: preparing a graphene material and a thermoplastic polymer into a graphene polymer composite film: preparing a graphene material, a thermoplastic polymer and a solvent into a solution of graphene and the thermoplastic polymer; the solvent is one or the combination of more of water, tetrahydrofuran, dichloroethane, tetrachloroethane, dichloromethane, trichloromethane, N-dimethylformamide, N-dimethylacetamide or N, N-dimethylpyrrolidone; putting the solution of the graphene and the thermoplastic polymer into an electrostatic spinning machine, carrying out single-nozzle electrostatic spinning or multi-nozzle conjugate electrostatic spinning at a liquid inlet speed of 0.2-5.0 ml/h under a voltage of 10-30 kV, depositing the solution on a receiving substrate, adjusting the spinning quality by controlling the liquid inlet speed and the voltage, adjusting the mass ratio of the graphene to the thermoplastic polymer, and controlling the fiber diameter to ensure the performance of the composite material, and removing the solvent at 50-100 ℃ to obtain the graphene polymer composite membrane, wherein the graphene polymer composite membrane has a microscopic fibrous porous structure, and the diameter of the fiber is 100-2500 nm.
The preparation method of the graphene polymer modified resin matrix composite material comprises the following steps of preparing the graphene polymer modified resin matrix composite material from the graphene polymer composite film and the resin matrix composite material: alternately paving m layers of graphene polymer composite films between n layers of resin-based composite materials, and obtaining the graphene polymer composite film modified resin-based composite material by a corresponding composite material forming method, wherein n is a natural number not less than 2, and m is a natural number less than n and not less than 1; the graphene material and the thermoplastic polymer exist between layers of the resin matrix composite material in the form of a graphene polymer composite film, so that the toughness of the resin matrix composite material is effectively improved, and the resin matrix composite material has better impact resistance; the graphene polymer composite membrane is formed by combining a microscopic porous structure formed by a graphene material and a thermoplastic polymer and a resin matrix composite material.
The preparation method of the graphene polymer modified resin-based composite material comprises the following steps of (1) preparing a solution, wherein the content of a graphene material in the solution relative to a solvent is 1-30 mg/ml, preferably 5-20 mg/ml, and preferably 5-10 mg/ml; the thermoplastic polymer is present in an amount of 0.01g/ml to 0.2g/ml relative to the solution.
The preparation method of the graphene polymer modified resin-based composite material comprises the following steps of adding the graphene material in the form of a dispersion liquid dispersed in a solvent, and uniformly dispersing the graphene material in the solvent through ultrasonic treatment to obtain a graphene material dispersion liquid; the thermoplastic polymer is added as a solution dissolved in the solvent.
Compared with the closest prior art, the invention has the following beneficial effects:
1) the graphene polymer composite membrane provided by the invention has a porous structure, so that the graphene polymer composite membrane is beneficial to being immersed into the porous structure when a resin matrix is heated to flow and is easy to discharge interlaminar volatile components, the combination between the resin and the modified graphene polymer composite membrane is improved, and the uniformity of the interlaminar structure of the material is improved;
2) the graphene polymer composite film provided by the invention has the graphene material and the thermoplastic polymer, so that the composite material can be toughened in a synergistic manner, and the excellent quality of the composite material is ensured;
3) the mechanical property of the graphene polymer composite film modified resin matrix composite material provided by the invention is remarkably improved due to the addition of the graphene polymer composite film between layers: the compression strength after impact is improved by more than 30 percent, and the heat resistance is improved.
Drawings
Fig. 1 is a scanning electron microscope image of a graphene polymer composite film having a smooth fiber surface;
fig. 2 is a scanning electron microscope image of the graphene polymer composite film in which graphene is attached to the surface of the fiber.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Dispersing 0.06g of graphene in 50ml of N, N-dimethylformamide, dispersing 1g of polyether sulfone resin in 10ml of N, N-dimethylformamide, and uniformly mixing and stirring to respectively prepare a graphene/polyether sulfone mixed solution; 2g of polyether sulfone resin is dissolved in 15ml of N, N-dimethyl formamide to prepare a polyether sulfone solution. The solution is subjected to conjugated electrostatic spinning through an electrostatic spinning machine to form a film, the spinning voltage of the graphene/polyether sulfone mixed solution is 20kV, the working distance is 20cm, and the liquid inlet speed is 1 ml/h; the spinning voltage of the polyether sulfone solution is 20kV, the working distance is 20cm, and the liquid inlet speed is 0.25 ml/h; and after spinning is finished, volatilizing in hot air at 80 ℃ to remove the organic solvent to form the graphene/polyether sulfone composite membrane. The graphene/polyether sulfone composite film toughened 5228A/T300-40B epoxy resin-based carbon fiber composite material is obtained by adopting a hot press molding process, and the compression strength after impact is 321 MPa.
Example 2
1g of graphene oxide is dispersed in 10ml of dichloroethane, 5g of polyether sulfone resin is dissolved in 40ml of dichloroethane, and the mixture is uniformly mixed and stirred to prepare a graphene/polysulfone mixed solution. Spinning the mixed solution into a film by an electrostatic spinning machine, wherein the spinning voltage is 12kV, the working distance is 15cm, and the liquid inlet speed is 1.5 ml/h; and after spinning is finished, volatilizing in hot air at 60 ℃ to remove the organic solvent to form the graphene polyether sulfone composite membrane. The graphene polyether sulfone composite film toughened 5228A/T300-40B epoxy resin-based carbon fiber composite material is prepared by adopting a vacuum bag pressing and forming process.
The compression strength after impact of the composite prepared in example 2 increased from 234MPa to 298MPa compared to 5228A/T300-40B epoxy resin based composites.
Example 3
Dispersing 0.5g of graphene oxide in 90ml of tetrahydrofuran, dissolving 1g of phenolphthalein modified polyether ketone in 10ml of tetrahydrofuran, and mixing and stirring uniformly to prepare a graphene/phenolphthalein modified polyether ketone mixed solution; 9g of phenolphthalein modified polyether ketone is dissolved in 100ml of tetrahydrofuran to prepare phenolphthalein modified polyether ketone mixed solution. And (3) carrying out conjugate spinning on the solution through an electrostatic spinning machine to form a film. The spinning voltage of the graphene/phenolphthalein modified polyether ketone mixed solution is 10kV, the working distance is 10cm, and the liquid inlet speed is 0.2 ml/h; the spinning voltage of the phenolphthalein modified polyether ketone mixed solution is 15kV, the working distance is 15cm, and the liquid inlet speed is 0.2 ml/h. And volatilizing to remove the organic solvent in a vacuum environment at 50 ℃ to form the graphene oxide/phenolphthalein modified polyether ketone composite membrane. The graphene oxide/phenolphthalein modified polyether ketone composite membrane toughened 5228A/T300-40B composite material is prepared by adopting an autoclave molding process. The post impact compressive strength of the composite prepared in example 3 increased from 234MPa to 318MPa compared to 5228A/T300-40B composite without the addition of graphene/polymer composite fiber membrane.
Example 4
The embodiment comprises the following steps: 0.5g of amino functionalized graphene is dispersed in 20ml of N, N-dimethylformamide, 20g of phenolphthalein modified polyether ketone is dissolved in 80ml of N, N-dimethylformamide, and the mixture is uniformly mixed and stirred to prepare an amino functionalized graphene/polyether ketone mixed solution. Spinning the mixed solution into a film by an electrostatic spinning machine, wherein the spinning voltage is 15kV, the working distance is 15cm, and the liquid inlet speed is 1 ml/h; and volatilizing in hot air at 100 ℃ to remove the organic solvent to form the amino functionalized graphene/polyether ketone composite membrane. Adopts a hot-press molding process, and the amino functionalized/graphene polyether ketone composite membrane toughens 5228A/T800-40B epoxy resin-based carbon fiber composite material. Compared with 5228A/T800-40B composite material without the graphene polymer composite fiber membrane, the compression strength of the composite material prepared in the example 4 after impact is improved from 157MPa to 359 MPa.
Example 5
1g of graphene is dispersed in 20ml of tetrahydrofuran, 10g of polyether-ether-ketone is dissolved in 80ml of tetrahydrofuran, and the graphene/polyether-ether-ketone mixed solution is prepared by uniformly mixing and stirring. Spinning the mixed solution into a film by an electrostatic spinning machine, wherein the spinning voltage is 15kV, the working distance is 20cm, and the liquid inlet speed is 1.5 ml/h; and volatilizing in hot air at 100 ℃ to remove the organic solvent to form the graphene/polyether-ether-ketone composite membrane. By adopting an RTM forming process, the graphene/polyether-ether-ketone composite film is used for toughening 5284RTM/G827 epoxy resin-based carbon fiber composite materials. Compared with a 5284RTM/G827 composite material without the graphene polymer composite fiber membrane, the compression strength after impact of the composite material prepared in example 5 is improved from 154MPa to 278 MPa.
Example 6
0.6g of graphene oxide is dispersed in 10ml of trichloromethane, 0.1g of polyetherimide is dissolved in 10ml of trichloromethane, and the mixture is uniformly mixed and stirred to prepare a graphene oxide/polyetherimide mixed solution. 0.5g of polyetherimide was dissolved in 10ml of chloroform to prepare a polyetherimide solution. Carrying out conjugate spinning on the mixed solution through an electrostatic spinning machine to form a film, wherein the spinning voltage of the graphene oxide/polyetherimide mixed solution is 20kV, the working distance is 20cm, and the liquid inlet speed is 5 ml/h; the spinning voltage of the polyetherimide solution is 30kV, the working distance is 30cm, and the liquid inlet speed is 5 ml/h. And volatilizing in hot air at 80 ℃ to remove the organic solvent to form the graphene oxide/polyetherimide composite membrane. The graphene oxide polyetherimide composite film toughened 5284RTM/U3160 composite material is prepared by adopting an RTM forming process.
Compared with a 5284RTM/U3160 composite material without the graphene polymer composite fiber membrane, the compression strength of the composite material prepared in example 7 after impact is improved from 155MPa to 258 MPa.
The embodiment fully proves that the graphene material and the thermoplastic polymer exist between layers of the resin-based composite material in the form of the graphene thermoplastic polymer composite film with the microscopic porous structure, the porous structure of the graphene polymer composite film is favorable for mutual combination with resin in the forming process, the uniformity between the layers of the composite material is improved, the interlayer performance of the composite material is enhanced, the mechanical property and the heat resistance of the resin-based composite material are remarkably improved, the compression strength after impact resistance is improved by at least 27.3 percent or even more than 100 percent compared with the prior art, and the graphene material and the thermoplastic polymer composite film have remarkable technical progress compared with the prior art.
The foregoing is merely a detailed description of the embodiments of the present invention, and some of the conventional techniques are not detailed. The scope of the present invention is not limited thereto, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention will be covered by the scope of the present invention. The protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (14)
1. A graphene polymer composite film modified resin matrix composite material is characterized in that: the graphene material and the thermoplastic polymer exist between resin matrix composite material layers in the form of a graphene polymer composite film; the graphene polymer composite membrane is a fibrous porous structure formed by a graphene material and a thermoplastic polymer, and the resin matrix composite material is dissolved in the porous structure and combined into a whole in the forming process; wherein the mass ratio of the graphene material to the thermoplastic polymer is 1: 1-50; more preferably 1: 5-40; more preferably 1: 10 to 20.
2. The graphene polymer composite film modified resin-based composite material according to claim 1, wherein: the diameter of the graphene polymer composite membrane fiber is 200-2000 nm.
3. The graphene polymer composite film modified resin-based composite material according to claim 1, wherein: the thickness of the graphene polymer composite film is 5-50 mu m.
4. The graphene polymer composite film modified resin-based composite material according to claim 1, wherein: the graphene material and the thermoplastic polymer are fully mixed, graphene and the polymer in the graphene thermoplastic polymer fiber are uniformly distributed, and the graphene is uniformly dispersed in a composite material interface.
5. The graphene polymer composite film modified resin-based composite material according to claim 1, wherein: the graphene material sheet is attached to the surface of the thermoplastic polymer fiber, so that the surface of the thermoplastic polymer fiber has a raised or wrinkled structure.
6. The graphene polymer composite film modified resin-based composite material according to claim 1, wherein: the graphene material in the graphene polymer composite film modified resin-based composite material is one or a combination of single-layer graphene, double-layer graphene oxide, reduced graphene oxide and functionalized graphene, and is selected from 3-10 layers of graphene, graphene oxide, reduced graphene oxide and functionalized graphene.
7. The graphene polymer composite film modified resin-based composite material according to claim 1, wherein: the thermoplastic polymer in the graphene polymer composite membrane modified resin matrix composite material is polyether ketone, polyether ether ketone, polyether imide, polysulfone, polyether sulfone, phenolphthalein modified polyether sulfone, polyphenylene sulfide, polyphenylene oxide or polyamide.
8. The graphene polymer composite film modified resin-based composite material according to claim 1, wherein: the resin-based composite material in the graphene polymer composite film modified resin-based composite material comprises an epoxy resin-based composite material, a cyanate resin-based composite material, a bismaleimide resin-based composite material and a polyimide resin-based composite material, and the epoxy resin-based composite material is preferably selected.
9. The graphene polymer composite film is characterized by being prepared from the following components in a mass ratio of 1: the 1-50 graphene material forms a fibrous porous structure by fusing or attaching on thermoplastic polymer fibers, wherein the fibrous diameter is 100-2000 nm.
10. A preparation method of a graphene polymer modified resin matrix composite material is characterized by comprising the following steps: preparing a graphene material, a thermoplastic polymer and a solvent into a mixed solution of graphene and the thermoplastic polymer or respectively preparing the graphene material and the thermoplastic polymer into solutions, then spinning to form a graphene polymer composite film, then placing the graphene polymer composite film between resin matrix composite material layers, and obtaining the graphene polymer modified resin matrix composite material by a corresponding composite material forming method.
11. The method for preparing the graphene polymer modified resin-based composite material according to claim 10, wherein:
the preparation process of the graphene polymer composite film comprises the following steps: preparing a graphene material and a thermoplastic polymer into a graphene polymer composite film, and preparing a solution of the graphene and the thermoplastic polymer by using the graphene material, the thermoplastic polymer and a solvent; the solvent is one or the combination of more of water, tetrahydrofuran, dichloroethane, tetrachloroethane, dichloromethane, trichloromethane, N-dimethylformamide, N-dimethylacetamide or N, N-dimethylpyrrolidone; and (2) putting the solution of the graphene and the thermoplastic polymer into an electrostatic spinning machine, performing single-nozzle electrostatic spinning/multi-nozzle conjugated electrostatic spinning at a liquid inlet speed of 0.2-5.0 ml/h under a voltage of 10-30 kV, depositing the solution on a receiving substrate, and removing the solvent at 50-100 ℃ to obtain the graphene polymer composite membrane, wherein the graphene polymer composite membrane has a microcosmic fibrous porous structure, and the diameter of the fiber is 100-2500 nm.
12. The method for preparing the graphene polymer modified resin-based composite material according to claim 10, wherein: the graphene polymer composite film and the resin-based composite material are prepared into the graphene polymer modified resin-based composite material by the following steps: alternately paving m layers of graphene polymer composite films between n layers of resin-based composite materials, and obtaining the graphene polymer composite film modified resin-based composite material by a corresponding composite material forming method, wherein n is a natural number not less than 2, and m is a natural number less than n and not less than 1; wherein the graphene material and the thermoplastic polymer exist between layers of the resin matrix composite material in the form of a graphene polymer composite film; the graphene polymer composite membrane is formed by combining a microscopic porous structure formed by a graphene material and a thermoplastic polymer and a resin matrix composite material.
13. The method for preparing the graphene polymer modified resin-based composite material according to claim 10, wherein: the content of the graphene material in the solution relative to the solvent is 1mg/ml-30mg/ml, preferably 5mg/ml-20mg/ml, preferably 5mg/ml-10 mg/ml; the thermoplastic polymer is present in an amount of 0.01g/ml to 0.2g/ml relative to the solution.
14. The method for preparing a graphene polymer modified resin-based composite material according to claim 13, wherein: adding the graphene material in the form of a dispersion liquid dispersed in the solvent, and uniformly dispersing the graphene material in the solvent through ultrasonic treatment to obtain a graphene material dispersion liquid; the thermoplastic polymer is added as a solution dissolved in the solvent.
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| US20150368439A1 (en) * | 2014-06-24 | 2015-12-24 | Enerage Inc. | Graphene Polymer Composite Material |
| CN105153640A (en) * | 2015-06-26 | 2015-12-16 | 中国航空工业集团公司北京航空材料研究院 | Preparation method for graphene polymer composite fiber film reinforced and toughened composite material |
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