CN109972400A - Modified sizing agent of a kind of graphene and its preparation method and application - Google Patents
Modified sizing agent of a kind of graphene and its preparation method and application Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/59—Polyamides; Polyimides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Abstract
The present invention relates to modified sizing agents of a kind of graphene and its preparation method and application, specifically disclose following steps: (1) preparing water-soluble polyamide resins；(2) hydrophilic graphene and alkaline stabiliser are dispersed in water, so that the pH of aqueous solution is 7~12, then by water soluble polyamide be added to more than aqueous solution in, obtain the modified sizing agent of graphene, the content of water soluble polyamide is 0.1wt%~50wt%, the additional amount of graphene or modified graphene is 0.001wt%~10wt%, and the additional amount of stabilizer is 0wt%~10wt%, and surplus is water.The sizing agent has good stability and water solubility, and environmental pollution is small, and production cost is low, and processing step is simple, can effectively improve the interface shear strength of carbon fiber reinforced polyamide based composites.
Description
[technical field]
The invention belongs to technical field of composite materials, in particular to a kind of graphene modified water-soluble polyamide sizing agent and its
Preparation method and application.
[background technique]
Carbon fiber have specific strength and modulus high (intensity or modulus/density), high temperature resistant, difficult burn into endurance, resist it is compacted
The a series of excellent performances such as change, electric-conductivity heat-conductivity high and low thermal coefficient of expansion, are current one of hot spot new materials.Carbon fiber
It is fragile material, in production and process, is easy fluffing through mechanical friction, or phenomena such as single wire fracture occur, makes carbon fiber
The strength reduction of dimension；Moreover, carbon fiber surface inertia, resin matrix cannot sufficiently soak carbon fiber, in composite material preparation
It is easy to produce hole, to influence the mechanical property of composite material.Therefore, it is necessary to specific processing technologys to be handled.
Starching is one of the main method to solve the above problems at present.Starching is conducive to carbon mono-filaments and integrates tow, just
In following process.Sizing agent can not only make up the defect of carbon fiber surface, improve filament strength, and be avoided that carbon fiber exists
Fracture or surface damage in process.In addition, sizing agent can also improve tree in carbon fiber reinforced polymer-based composite material
Aliphatic radical body is to the wellability of carbon fiber, to improve interface bond strength between the two.
Fibre reinforced thermoplastic composite (CFRTP) has shock resistance, high temperature resistant, short molding cycle, recyclable benefit
With the advantages that, be widely used in the fields such as space flight and aviation, defence and military, auto industry, sports goods.But be commercialized at present
Sizing agent is mainly the heat cured sizing agent based on epoxy resin, is matched with epoxy resin-base composite material.It is applied to
There is a problem of that compatibility is bad when thermoplastic resin based composite material, while being unable to satisfy the requirement of its high temperature process, therefore
It is not suitable for the interface optimization of fibre reinforced thermoplas tic resin composite.
In thermoplastic polymer kind, polyamide 6 (nylon 6) is a kind of polymerization that hemicrystalline main chain contains a large amount of amido bonds
Object has the characteristics that good excellent mechanical performance, shock resistance, wearability, self-lubricating, resistant to chemical etching, has been widely used for
The components such as gear, pulley, blade, covering, floor.6 polymer matrix composites of carbon fiber reinforced polyamide are in lightweight skill
Art field is expected to get a lot of applications, but since polyamide 6 viscous state temperature is high, melt viscosity is big and carbon fiber
The problems such as matrix compatibility is bad leads to its processing difficulties, and composite material interface performance is poor, directly reduces the machine of composite material
Tool performance.
To solve the above-mentioned problems, need to develop a kind of carbon fiber sizing agent for thermoplastic nylon matrix, to mention
The compatibility and interface shear strength of high carbon fiber and nylon matrix.
[summary of the invention]
To solve the above-mentioned problems, the present invention provides a kind of modified sizing agent of graphene, carbon fiber and Buddhist nun be can be improved
The compatibility and interface shear strength of imperial matrix.
The present invention also provides the preparation method of the modified sizing agent of above-mentioned graphene, preparation process simple process, environment friends
Good, production cost is low.
The present invention also provides the applications of the modified sizing agent of above-mentioned graphene, can effectively improve polyamide resin aliphatic radical composite wood
The interface shear strength (IFSS) of material.
The technical scheme is that
A kind of modified sizing agent of graphene, which is characterized in that comprising 0.1wt%~50wt% water-soluble polyamide resins,
The additional amount of 0.001wt%~10wt% graphene, 0wt%~10wt% stabilizer, surplus are water；The graphene is surface
Hydrophilic graphite containing hydroxyl, amino, carboxyl, ester group, aldehyde radical, ether, hydrazide group, amide groups, phosphate or sulfonic group
Black alkene；The stabilizer is ammonium hydroxide or weakly alkaline sulfonate, sulfuric ester salt form anionic surfactant.
Further, above-mentioned hydrophilic graphene is graphene oxide, gallic acid reduced graphene, glycidol ether surpass
Branched modification graphene or daiamid modified graphene.
Further, above stabilizer is weakly alkaline ammonium hydroxide, ammonium lauryl sulfate, dodecyl ether sulfate ammonium
(AESA), one or more of lauryl sodium sulfate, neopelex.
Further, above-mentioned water-soluble polyamide resins are prepared by the following method: by annular diamine and binary acid point
It is not dissolved in solvent a, is configured to the uniform solution of 5wt%~50wt%, the two equimolar is blended, 40~60 DEG C of stirrings,
Reaction time is 1-6 hours, removes solvent, is extracted after nylon salt crystallization, removes residual monomer, obtains water-soluble Buddhist nun after dry
Imperial salt；Water-soluble nylon salt is dissolved in solvent b, second of nylon salt c is added, mixing nylon salt is configured to 50wt%
The solution of~90wt% adds the end-capping reagent of 0.1~1.8mol% of nylon salt total amount, is passed through nitrogen, and 200~215 DEG C anti-
It answers 2~4h precondensation to 0.8~0.9 extent of reaction, vapor is persistently discharged in the process；It is warming up to 250~270 DEG C of further contractings
It is poly-, and continue that vapor is discharged, until reacting to system viscosity >=1000mPas, reaction terminates, and cooling, extracting removes not anti-
Monomer is answered, drying is simultaneously sliced, and obtains water-soluble polyamide resins.
Further, it is 0~99mol% that above-mentioned nylon salt c, which accounts for the ratio of nylon salt total amount,.
Further, above-mentioned annular diamine is piperazine, 1-2- aminoethyl piperazine, 1- (5- Aminopentyl) piperazine, high piperazine
The bis- aminopropyl piperazines of piperazine, 1,4-, isophorone diamine, 1,2- cyclohexanediamine, 1,4- cyclohexanediamine, R-3 amino piperidine, S-3 ammonia
One or more of phenylpiperidines, 2,6- lupetazin.
Further, above-mentioned binary acid is succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, certain herbaceous plants with big flowers two
One or more of acid, dodecanedioic acid, cyclohexane dicarboxylic acid, maleic acid.
Further, above-mentioned solvent a be water, ethyl alcohol, methanol, propyl alcohol, glycerol, ethylene glycol, propylene glycol, isobutanol, ether,
One or more of tetrahydrofuran；The solvent b is water, ethyl alcohol and its mixed liquor.
Further, above-mentioned second of nylon salt c is 6 salt of nylon, nylon salt, Nylon-1010 Salt, nylon 1212 salt, Buddhist nun
One or more of imperial 610 salt, nylon 612 salt, nylon 46 salt, 12 salt of nylon, nylon 11 salt.
Further, above-mentioned end-capping reagent is monofunctional carboxylic acids.
The preparation method of the modified sizing agent of above-mentioned graphene, which is characterized in that comprise the steps of:
(1) annular diamine and binary acid are dissolved in respectively in solvent a, are configured to the uniform molten of 5wt%~50wt%
The two equimolar is blended liquid, and 40~60 DEG C of stirrings, the reaction time is 1-6 hours, removes solvent, takes out after nylon salt crystallization
It mentions, removes residual monomer, obtain water-soluble nylon salt after dry；Water-soluble nylon salt is dissolved in solvent b, adds second
Kind of nylon salt c, the solution for nylon salt will be mixed being configured to 50wt%~90wt%, add nylon salt total amount 0.1~
The end-capping reagent of 1.8mol%, is passed through nitrogen, 200~215 DEG C of reaction 2~4h precondensations to 0.8~0.9 extent of reaction, in the process
Vapor is persistently discharged；250~270 DEG C of further polycondensations are warming up to, and continue that vapor is discharged, until reaction to system viscosity
>=1000mPas, reaction terminate, cooling, and extracting removes unreacted monomer, and drying is simultaneously sliced, and obtain water soluble polyamide tree
Rouge；
(2) hydrophilic graphene is distributed in water, the aqueous solution that concentration is 0.001~10wt% is made into, using steady
Determine agent and the pH of solution is adjusted to 7~12, forms uniform graphene solution；
(3) water-soluble polyamide resins that step (1) obtains are dissolved in the graphene solution of step (2), are prepared into
To the modified sizing agent of graphene.
The application of the modified sizing agent of above-mentioned graphene, which is characterized in that the sizing agent is used for for polyamide substrate
The manufacture field of carbon fibre composite, polyamide substrate for example nylon 6, nylon66 fiber, nylon 1010, nylon 1212, nylon 610,
Nylon 612, nylon 46, nylon 12, nylon 11, aromatic nylon and semi-aromatic nylon etc. but unlimited above several.
The invention has the following beneficial technical effects:
Preparation process simple process of the present invention, environmental-friendly, production cost is low, and the sizing agent of preparation is aqueous sizing agent,
Volatilization is divided into vapor in drying process, can be reduced the pollution to environment and human body compared to solvent-borne type sizing agent；Of the invention
The modified sizing agent of graphene can effectively improve the compatibility of carbon fiber and polyamide, so that polyamide resin composite material
It is easily worked；The modified sizing agent of graphene of the invention can effectively improve the interface of carbon fiber reinforced polyamide based composites
Shear strength (IFSS).
[Detailed description of the invention]
Fig. 1 is the electromicroscopic photograph that the micro- unsticking pattern of 6 composite material interface of carbon fiber/polyamide amine is commercialized in comparative example 1.
Fig. 2 is the electromicroscopic photograph of the micro- unsticking pattern in modified carbon fiber in example 2/polyamide 6 composite material interface.
Fig. 3 is the electromicroscopic photograph that 6 composite material section of carbon fiber/polyamide amine is commercialized in comparative example 2.
Fig. 4 is modified carbon fiber in example 6/polyamide 6 composite material section electromicroscopic photograph.
[specific embodiment]
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment provided below is not intended to limit the invention covered range, and described step is also not use
Sequence is executed to limit its.Those skilled in the art combine existing common knowledge to do conspicuous improvement to the present invention, also fall
Enter the present invention claims protection scope within.
A kind of modified sizing agent of graphene, comprising 0.1wt%~50wt% water-soluble polyamide resins, 0.001wt%~
The additional amount of 10wt% graphene, 0wt%~10wt% stabilizer, surplus are water；The graphene is that hydroxyl, ammonia are contained in surface
Base, carboxyl, ester group, aldehyde radical, ether, hydrazide group, amide groups, phosphate or sulfonic group hydrophilic graphene；It is described steady
Determining agent is ammonium hydroxide or weakly alkaline sulfonate, sulfuric ester salt form anionic surfactant.
Further, the average grain diameter of the modified sizing agent of above-mentioned graphene is between 10nm~3000nm.
Further, above-mentioned hydrophilic graphene is graphene oxide, gallic acid reduced graphene, glycidol ether surpass
Branched modification graphene or daiamid modified graphene；Above stabilizer is weakly alkaline ammonium hydroxide, ammonium lauryl sulfate, ten
One or more of dialkyl group ether sulfate ammonium (AESA), lauryl sodium sulfate, neopelex.
The modified sizing agent of above-mentioned graphene is prepared by the following method:
(1) water-soluble polyamide resins are prepared: annular diamine and binary acid are dissolved in respectively in solvent a, are configured to
The two equimolar is blended the solution of 5wt%~50wt%, and 40~60 DEG C of constant temperature stirrings, the reaction time is 1-6 hours, big portion
After the volatilization of point solvent, solution gradually becomes sticky, and soxhlet type in acetone after vacuum drying, crystallization obtains water-soluble after dry
Property nylon salt；Above-mentioned water-soluble nylon salt is dissolved in solvent b, second of nylon salt c is added, nylon salt c accounts for nylon salt
Sum-rate is 0~99mol%, and mixing nylon salt is configured to the concentrated solution of 50wt%~90wt%, it is total to add nylon salt
The end-capping reagent of 0.1~1.8mol% of amount, is passed through nitrogen, 200~215 DEG C of reaction 2~4h precondensations to 0.8~0.9 reaction interval
Vapor is constantly discharged in degree in the process.250~270 DEG C of further polycondensations are warming up to, and vapor is constantly discharged, until reaction
Increase suddenly to system viscosity, reaction terminates, and polymer is shifted and cooled down, and extracting, drying are simultaneously sliced, and obtains water-soluble polyamides
Polyimide resin.(2) hydrophilic graphene is distributed in water under the action of ultrasonic wave or stirring, be made into concentration be 0.001~
The aqueous solution of 10wt%.The pH of solution is adjusted to 7~12 using stabilizer, forms the graphene solution of stable homogeneous, it is water-soluble
Property polyamide is dissolved in stable graphene weak solution, and graphene modified water-soluble polyamide carbon fiber starching is prepared
Agent.
Further, above-mentioned annular diamine is piperazine, 1-2- aminoethyl piperazine, 1- (5- Aminopentyl) piperazine, high piperazine
The bis- aminopropyl piperazines of piperazine, 1,4-, isophorone diamine, 1,2- cyclohexanediamine, 1,4- cyclohexanediamine, R-3 amino piperidine, S-3 ammonia
One or more of phenylpiperidines, 2,6- lupetazin.
Further, above-mentioned binary acid is succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, certain herbaceous plants with big flowers two
One or more of acid, dodecanedioic acid, cyclohexane dicarboxylic acid, maleic acid.
Further, above-mentioned solvent a be water, ethyl alcohol, methanol, propyl alcohol, glycerol, ethylene glycol, propylene glycol, isobutanol, ether,
One or more of tetrahydrofuran；The solvent b is water, ethyl alcohol and its mixed liquor.
Further, above-mentioned second of nylon salt c is 6 salt of nylon, nylon salt, Nylon-1010 Salt, nylon 1212 salt, Buddhist nun
One or more of imperial 610 salt, nylon 612 salt, nylon 46 salt, 12 salt of nylon, nylon 11 salt.
Further, above-mentioned end-capping reagent is monofunctional carboxylic acids.
Examples 1 to 7 prepare water-soluble polyamide resins concrete component and reaction condition is as shown in table 1.Wherein, table 1
Middle nylon salt c concentration is nylon salt c: the ratio of the nylon salt of water soluble polyamide, end-capping reagent are acetic acid.Examples 1 to 7
Concrete component and the relevant parameter for preparing the modified sizing agent of graphene are as shown in table 2, simultaneously include solid content and use in table 2
The average grain diameter that dynamic light scattering method measures.
1 Examples 1 to 7 of table prepares water-soluble polyamide resins concrete component and reaction condition
The concrete component and relevant parameter for preparing the modified sizing agent of graphene of 2 Examples 1 to 7 of table
Composite material interface performance test experiment
Method for sizing: Jiang Dongli (Toray) T700 carbon fiber wire takes off surface size agent with acetone extraction；On homemade
The sizing agent of suitable solid content is added in pulp grinder, carbon fiber wire is dried after impregnating in glue groove by heating roller.
(IFSS) sample preparation of composite material interface shear strength and test method:
(1) using the flourish composite material interface device for evaluating performance sample preparation in Japan east: under nitrogen protection dripping melted nylon 6
It is attached on carbon mono-filaments, nylon 6 forms microballon by surface tension effects in carbon fiber surface, solidifies after cooling.
(2) tested using the flourish composite material interface device for evaluating performance in Japan east: cutter is micro- by 6 microballon of nylon and carbon fiber
Unsticking, and interface shear strength (IFSS) is obtained, the results are shown in Table 3.
The carbon fiber that comparative example 1 uses is T700 destarch silk, and it is T700 that comparative example 2, which uses,.
3 composite material interface performance test experimental result of table
The result shows that: graphene modified water-soluble polyamide sizing agent can significantly improve carbon fiber reinforced polyamide composite material
Interfacial bond property.Unsticking fiber surface has remained a large amount of matrix resin fragments and shows carbon fiber and matrix resin in attached drawing 2
Between adhesion strength it is high, interface performance greatly improves, and wellability is good between carbon fiber and polyamide in attached drawing 4, and porosity is low
Illustrate that the compatibility of carbon fiber and polyamide can be improved in the graphene modified water-soluble polyamide sizing agent, so that polyamide
Composite material is easily worked.
Claims (12)
1. a kind of modified sizing agent of graphene, which is characterized in that comprising 0.1wt%~50wt% water-soluble polyamide resins,
The additional amount of 0.001wt%~10wt% graphene, 0wt%~10wt% stabilizer, surplus are water；The graphene is surface
Hydrophilic graphite containing hydroxyl, amino, carboxyl, ester group, aldehyde radical, ether, hydrazide group, amide groups, phosphate or sulfonic group
Black alkene；The stabilizer is ammonium hydroxide or weakly alkaline sulfonate, sulfuric ester salt form anionic surfactant.
2. the modified sizing agent of graphene according to claim 1, which is characterized in that the hydrophilic graphene is oxidation stone
Black alkene, gallic acid reduced graphene, the hyperbranched modified graphene of glycidol ether or daiamid modified graphene.
3. the modified sizing agent of graphene according to claim 1, which is characterized in that the stabilizer is weakly alkaline ammonia
One of water, ammonium lauryl sulfate, dodecyl ether sulfate ammonium, lauryl sodium sulfate, neopelex
Or it is several.
4. the modified sizing agent of graphene according to claim 1, which is characterized in that the water-soluble polyamide resins pass through
Following methods preparation: annular diamine and binary acid are dissolved in respectively in solvent a, the uniform of 5wt%~50wt% is configured to
The two equimolar is blended solution, and 40~60 DEG C of stirrings, the reaction time is 1-6 hours, removes solvent, after nylon salt crystallization
Extracting removes residual monomer, obtains water-soluble nylon salt after dry；Water-soluble nylon salt is dissolved in solvent b, adds
Two kinds of nylon salt c will mix nylon salt and be configured to the solution of 50wt%~90wt%, add nylon salt total amount 0.1~
The end-capping reagent of 1.8mol%, is passed through nitrogen, and vapor is persistently discharged in 200~215 DEG C of reaction 2~4h precondensations in the process；Heating
To 250~270 DEG C of further polycondensations, and continue that vapor is discharged, until reaction to system viscosity >=1000mPas, reaction knot
Beam, cooling, extracting removes unreacted monomer, and drying is simultaneously sliced, and obtains water-soluble polyamide resins.
5. the modified sizing agent of graphene according to claim 4, which is characterized in that the nylon salt c accounts for nylon salt total amount
Ratio be 0~99mol%.
6. the modified sizing agent of graphene according to claim 4, which is characterized in that the annular diamine is piperazine, 1-
2- aminoethyl piperazine, 1- (5- Aminopentyl) piperazine, homopiperazine, the bis- aminopropyl piperazines of 1,4-, isophorone diamine, 1,2- hexamethylene
One or more of diamines, 1,4- cyclohexanediamine, R-3 amino piperidine, S-3 amino piperidine, 2,6- lupetazin.
7. the modified sizing agent of graphene according to claim 4, which is characterized in that the binary acid is succinic acid, penta 2
One of acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, cyclohexane dicarboxylic acid, maleic acid
Or it is several.
8. the modified sizing agent of graphene according to claim 4, which is characterized in that the solvent a be water, ethyl alcohol, methanol,
One or more of propyl alcohol, glycerol, ethylene glycol, propylene glycol, isobutanol, ether, tetrahydrofuran；The solvent b is water, ethyl alcohol
And its mixed liquor.
9. the modified sizing agent of graphene according to claim 4, which is characterized in that second of nylon salt c is nylon 6
Salt, nylon salt, Nylon-1010 Salt, nylon 1212 salt, nylon 610 salt, nylon 612 salt, nylon 46 salt, 12 salt of nylon, nylon
One or more of 11 salt.
10. the modified sizing agent of graphene according to claim 4, which is characterized in that the end-capping reagent is simple function group carboxylic
Acid.
11. the preparation method of the modified sizing agent of graphene as described in claim 1-10, which is characterized in that include following step
It is rapid:
(1) annular diamine and binary acid are dissolved in respectively in solvent a, are configured to the uniform solution of 5wt%~50wt%, it will
The two equimolar is blended, and 40~60 DEG C of stirrings, the reaction time is 1-6 hours, removes solvent, extracts, removes after nylon salt crystallization
Residual monomer is removed, obtains water-soluble nylon salt after dry；Water-soluble nylon salt is dissolved in solvent b, second of Buddhist nun is added
Mixing nylon salt is configured to the solution of 50wt%~90wt%, adds 0.1~1.8mol% of nylon salt total amount by imperial salt c
End-capping reagent, be passed through nitrogen, vapor is persistently discharged in 200~215 DEG C of reaction 2~4h precondensations in the process；It is warming up to 250~
270 DEG C of further polycondensations, and continue that vapor is discharged, until reacting to system viscosity >=1000mPas, reaction terminates, cold
But, extracting removes unreacted monomer, and drying is simultaneously sliced, and obtains water-soluble polyamide resins；
(2) hydrophilic graphene is distributed in water, is made into the aqueous solution that concentration is 0.001~10wt%, uses stabilizer
The pH of solution is adjusted to 7~12, forms uniform graphene solution；
(3) water-soluble polyamide resins that step (1) obtains are dissolved in the graphene solution of step (2), stone is prepared
The modified sizing agent of black alkene.
12. the application of the modified sizing agent of graphene as described in claim 1-10, which is characterized in that the sizing agent is used for needle
To the manufacture field of the carbon fibre composite of polyamide substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711456291.5A CN109972400B (en) | 2017-12-28 | 2017-12-28 | Graphene modified sizing agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711456291.5A CN109972400B (en) | 2017-12-28 | 2017-12-28 | Graphene modified sizing agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109972400A true CN109972400A (en) | 2019-07-05 |
| CN109972400B CN109972400B (en) | 2022-04-12 |
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