CN107722595B - Preparation method of fiber-graphene-thermoplastic polyarylether multi-scale composite material - Google Patents
Preparation method of fiber-graphene-thermoplastic polyarylether multi-scale composite material Download PDFInfo
- Publication number
- CN107722595B CN107722595B CN201710991858.2A CN201710991858A CN107722595B CN 107722595 B CN107722595 B CN 107722595B CN 201710991858 A CN201710991858 A CN 201710991858A CN 107722595 B CN107722595 B CN 107722595B
- Authority
- CN
- China
- Prior art keywords
- graphene
- fiber
- polyarylether
- thermoplastic
- graphene oxide
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
A preparation method of a fiber-graphene-thermoplastic polyarylether multi-scale composite material belongs to the technical field of materials, and comprises the following steps: (1) adding graphene oxide into a solvent N, N-dimethylacetamide for dispersion; (2) adding thermoplastic polyarylether resin into a solvent N, N-dimethylacetamide and uniformly stirring; (3) mixing and stirring the graphene oxide dispersion solution and a thermoplastic polyarylether resin solution, and performing ultrasonic dispersion; (4) placing the continuous fibers in a dipping solution, fully dipping, drying at 220 +/-10 ℃, and simultaneously carrying out in-situ thermal reduction on the graphene oxide; (5) and (5) placing the mixture into a mould for forming. The preparation method is scientific and reasonable, simple in process and strong in operability, and the application range of the preparation method is greatly expanded.
Description
Technical Field
the invention belongs to the technical field of materials, and particularly relates to a preparation method of a fiber-graphene-thermoplastic polyarylether multi-scale composite material.
background
Polyaryletherketone (PEK-C) containing phenolphthalein side groups, polyarylethersulfone (PES-C) containing phenolphthalein side groups and polyarylethersulfone ketone (PPESK) containing phthalazinone biphenyl structures are polyaryletherhigh-performance thermoplastic resins which are self-developed by China and have excellent mechanical properties, high temperature resistance and processability, and are developed rapidly in recent years.
Fiber composite materials using high-performance thermoplastic resins as matrix have higher elastic modulus and interface bonding strength, and compared with thermosetting composite materials, the fiber composite materials have the advantages of high impact damage resistance, long prepreg storage period, recyclability and the like, and are receiving more and more attention.
Graphene is a two-dimensional crystal of carbon atoms of a single atom thickness, and is considered as a basic structural unit of fullerene, carbon nanotube and graphite. Graphene has high hardness, high strength, low thermal expansion coefficient, high electrical conductivity, high thermal conductivity, extremely high length-diameter ratio and ultra-large specific surface area, and the preparation method is various and relatively mature, so that graphene is generally regarded as an ideal polymer modified filler, and has more obvious advantages compared with other carbon nano materials.
However, graphene sheets have strong pi-pi interaction, are very inert in surface, are not compatible with organic matters, are very easy to agglomerate in polymers, and the composite material cannot fully exert the excellent performance of graphene. At present, the literature at home and abroad mainly reports that the graphene oxide or functionalized graphene oxide is used for modifying and researching a thermoplastic resin matrix, and the graphene is used for modifying a continuous fiber reinforced high-performance polyarylether resin matrix composite material, and the literature is rarely reported.
disclosure of Invention
The invention aims to provide a preparation method of a fiber-graphene-thermoplastic polyarylether multi-scale composite material, which comprises the steps of dispersing graphene oxide in a solvent, mixing the graphene oxide with a thermoplastic polyarylether resin solution, carrying out ultrasonic dispersion to form an impregnation solution, fully impregnating a fiber material with the impregnation solution, carrying out in-situ thermal reduction on the graphene oxide while heating to remove the solvent, and finally carrying out hot press molding on the obtained prepreg to improve the performance of the fiber-reinforced high-performance thermoplastic polyarylether resin composite material.
the method of the invention comprises the following steps:
1. Adding graphene oxide into a solvent N, N-dimethylacetamide, and performing ultrasonic dispersion for 1-2 hours to form a graphene oxide dispersion solution;
2. Adding thermoplastic polyarylether resin into a solvent N, N-dimethylacetamide, and uniformly stirring to prepare a thermoplastic polyarylether resin solution with the mass concentration of 10-35%; the thermoplastic polyarylether resin is selected from polyarylether ketone resin containing phenolphthalein side groups, polyarylether sulfone resin containing phenolphthalein side groups or polyarylether sulfone ketone resin containing phthalazinone biphenyl structures;
3. Mixing the graphene oxide dispersion solution with a thermoplastic polyarylether resin solution, stirring for 1-2 h, and then ultrasonically dispersing for 1-2 h to prepare an impregnation solution; the graphene oxide in the dipping solution accounts for 0.05-0.75% of the total mass of the polyarylether resin;
4. Placing the continuous fibers in an impregnation solution, fully impregnating the continuous fibers until the fibers in the continuous fibers are soaked, taking out the continuous fibers, drying the continuous fibers for 2-3 hours at the temperature of 220 +/-10 ℃, removing the solvent, and simultaneously carrying out in-situ thermal reduction on graphene oxide to obtain a graphene-containing prepreg;
5. And (3) placing the prepreg containing the graphene into a mould, and preparing the fiber-graphene-thermoplastic polyarylether multi-scale composite material by compression molding or autoclave molding.
The continuous fiber is selected from glass fiber, carbon fiber, aramid fiber or PBO fiber.
The continuous fiber has a filament diameter of 2 to 18 μm.
The particle size of graphene in the fiber-graphene-thermoplastic polyarylether composite material is 5-400 nm.
in the method, the temperature is 310-440 ℃, the pressure is 0.5-10 MPa, and the molding time is 3-4 h during compression molding or autoclave molding.
In the above steps 1 and 3, the ultrasonic frequency selected for ultrasonic dispersion is 40 Hz.
The surface of graphene oxide adopted by the invention contains a large amount of oxygen-containing functional groups such as hydroxyl, carboxyl, epoxy and the like, and can be uniformly dispersed in water and solvents such as N, N-dimethylacetamide and the like, the graphene oxide is uniformly dispersed in soluble polyarylether resin matrixes such as PEK-C, PES-C or PPESK and the like in a solution blending mode, after fiber impregnation, the graphene oxide is subjected to in-situ reduction while the solvent is removed by drying, so that a prepreg containing the graphene is obtained, and the prepreg is used for preparing a multi-scale composite material with excellent comprehensive performance; in the composite material, micron-sized fibers with different sizes and nano-sized graphene jointly form a reinforcement to form a multi-scale structure.
The invention has the following beneficial effects: (1) graphene oxide is uniformly dispersed in N, N-dimethylacetamide through ultrasound, and after the graphene oxide is mixed with a resin solution, the dispersion of the graphene oxide in a resin matrix is greatly promoted; (2) fully soaking continuous fibers or fiber fabrics in a resin mixed solution, heating in an oven to remove a solvent, simultaneously carrying out in-situ thermal reduction on graphene oxide, and obtaining a prepreg with uniformly dispersed graphene under the condition of no need of a reducing agent; (3) the prepared multi-scale composite material has excellent performance, and the interlaminar shear strength, the bending modulus and the impact toughness are obviously improved; the preparation method is scientific and reasonable, simple in process and strong in operability, greatly expands the application range of the composite material and has remarkable social and economic benefits.
drawings
fig. 1 is a graph of the thermal weight loss of graphene oxide used in the present invention.
Detailed Description
the graphene oxide adopted in the implementation of the invention is a commercially available product.
the N, N-dimethylacetamide used in the examples of the present invention is a commercially available analytical reagent.
the polyaryletherketone resin (PEK-C) containing the phenolphthalein side group, the polyarylethersulfone resin (PES-C) containing the phenolphthalein side group and the polyarylethersulfone ketone resin (PPESK) containing the phthalazinone biphenyl structure adopted in the embodiment of the invention are commercially available products.
The glass fiber, the carbon fiber, the aramid fiber and the PBO fiber adopted in the embodiment of the invention are commercially available products.
the interlayer shear strength in the examples of the invention was tested using the standard ASTM D2344.
The standard for testing the bending strength and the bending modulus in the embodiment of the invention is GB/T1449.
the standard for testing impact toughness in the examples of the invention is GB/T1451.
the monofilament diameter of the continuous fiber in the embodiment of the invention is 2-18 μm.
In the embodiment of the invention, the particle size of the graphene oxide is 5-400 nm.
In the embodiment of the invention, the particle size of graphene in the fiber-graphene-thermoplastic polyarylether composite material is 5-400 nm.
The ultrasonic frequency selected during ultrasonic dispersion in the embodiment of the invention is 40 Hz.
In the embodiment of the invention, the unmodified fiber-thermoplastic polyarylether composite material is prepared by adopting the scheme of the same steps without adding graphene oxide (in-situ thermal reduction reaction is not generated), and the performance is compared.
Example 1
adding graphene oxide into a solvent N, N-dimethylacetamide, and performing ultrasonic dispersion for 1h to form a graphene oxide dispersion solution;
adding thermoplastic polyarylether resin into a solvent N, N-dimethylacetamide, and uniformly stirring to prepare a thermoplastic polyarylether resin solution with the mass concentration of 10%; the thermoplastic polyarylether resin is PEK-C;
mixing the graphene oxide dispersion solution with a thermoplastic polyarylether resin solution, stirring for 2 hours, and then carrying out ultrasonic dispersion for 1.5 hours to prepare an impregnation solution; the graphene oxide in the dipping solution accounts for 0.05 percent of the total mass of the polyarylether resin;
placing the continuous fibers in an impregnation solution, fully impregnating the continuous fibers until the fibers in the continuous fibers are soaked, taking out the continuous fibers, drying the continuous fibers for 2 hours at the temperature of 220 +/-10 ℃, removing the solvent, and simultaneously carrying out in-situ thermal reduction on graphene oxide to obtain a graphene-containing prepreg; the continuous fiber is glass fiber;
In the in-situ thermal reduction process, the thermal weight loss curve of the graphene oxide is shown in fig. 1, and the fastest weight loss rate of the graphene oxide at 220 ℃ can be seen, which indicates that a large number of oxygen-containing groups on the surface of the graphene oxide are decomposed and removed, and the graphene oxide undergoes an obvious reduction reaction;
Placing the prepreg containing graphene in a mould, and carrying out compression molding to prepare a fiber-graphene-thermoplastic polyarylether multi-scale composite material; the temperature and pressure for compression molding are 310 ℃, 10MPa and the molding time is 4 h;
the obtained fiber-graphene-thermoplastic polyarylether multi-scale composite material has the interlaminar shear strength of 85.5MPa, the bending strength of 1765MPa, the bending modulus of 68GPa and the impact toughness of 14.8KJ/m2(ii) a Compared with unmodified fiber-thermoplastic polyarylether composite material, the composite material is respectively improved by 31.1%, 23.9%, 23.6% and 42.3%.
Example 2
the method is the same as example 1, except that:
(1) Carrying out ultrasonic dispersion for 1.5h to prepare a graphene oxide dispersion solution;
(2) The mass concentration of the thermoplastic polyarylether resin solution is 20 percent; the thermoplastic polyarylether resin is PES-C;
(3) mixing and stirring the graphene oxide dispersion solution and the thermoplastic polyarylether resin solution for 1.5h, and performing ultrasonic dispersion for 1 h; the graphene oxide in the dipping solution accounts for 0.25 percent of the total mass of the polyarylether resin;
(4) Putting the continuous fibers into a dipping solution, fully dipping, taking out, and drying for 3h at 220 +/-10 ℃; the continuous fiber is made of carbon fiber;
(5) Preparing a fiber-graphene-thermoplastic polyarylether multi-scale composite material by autoclave molding; the molding temperature is 350 ℃, the pressure is 5MPa, and the time is 3.5 h;
(6) the obtained fiber-graphene-thermoplastic polyarylether multi-scale composite material has the interlaminar shear strength of 104.5MPa, the bending strength of 1868MPa, the bending modulus of 115Gpa and the impact toughness of 13.2KJ/m2(ii) a Compared with unmodified fiber-thermoplastic polyarylether composite material, the composite material is improved by 33.1%, 41.5%, 64.3% and 37.5%.
Example 3
The method is the same as example 1, except that:
(1) Carrying out ultrasonic dispersion for 2 hours to prepare a graphene oxide dispersion solution;
(2) The mass concentration of the thermoplastic polyarylether resin solution is 30 percent; the thermoplastic polyarylether resin is PPESK;
(3) mixing and stirring the graphene oxide dispersion solution and the thermoplastic polyarylether resin solution for 1 hour, and performing ultrasonic dispersion for 2 hours; the graphene oxide in the dipping solution accounts for 0.5 percent of the total mass of the polyarylether resin;
(4) Putting the continuous fibers into the dipping solution, fully dipping the continuous fibers, taking the continuous fibers out, and drying the continuous fibers for 2.5 hours at the temperature of 220 +/-10 ℃; the continuous fiber is aramid fiber;
(5) Preparing a fiber-graphene-thermoplastic polyarylether multi-scale composite material by compression molding; the molding temperature is 410 ℃, the pressure is 2MPa, and the time is 3 h;
(6) the obtained fiber-graphene-thermoplastic polyarylether multi-scale composite material has the interlaminar shear strength of 56.2MPa, the bending strength of 678MPa, the bending modulus of 60.2GPa and the impact toughness of 21.5KJ/m2(ii) a Compared with unmodified fiber-thermoplastic polyarylether composite material, the composite material is respectively improved by 43.3%, 30.3%, 41.6% and 22.9%.
Example 4
The method is the same as example 1, except that:
(1) carrying out ultrasonic dispersion for 1.5h to prepare a graphene oxide dispersion solution;
(2) the mass concentration of the thermoplastic polyarylether resin solution is 35 percent; the thermoplastic polyarylether resin is PEK-C;
(3) Mixing and stirring the graphene oxide dispersion solution and the thermoplastic polyarylether resin solution for 1.5h, and performing ultrasonic dispersion for 1.5 h; the graphene oxide in the dipping solution accounts for 0.75 percent of the total mass of the polyarylether resin;
(4) putting the continuous fibers into the dipping solution, fully dipping the continuous fibers, taking the continuous fibers out, and drying the continuous fibers for 2.5 hours at the temperature of 220 +/-10 ℃; the continuous fiber is PBO fiber;
(5) preparing a fiber-graphene-thermoplastic polyarylether multi-scale composite material by autoclave molding; the molding temperature is 440 ℃, the pressure is 0.5MPa, and the time is 3.5 h;
(6) The interlaminar shear strength of the obtained fiber-graphene-thermoplastic polyarylether multi-scale composite material is 42.6MPa, the bending strength is 645MPa, the bending modulus is 48.6GPa, and the impact toughness is 19.8KJ/m2(ii) a Compared with unmodified fiber-thermoplastic polyarylether composite material, the composite material is respectively improved by 59.6%, 40.2%, 51.8% and 26.9%.
Claims (3)
1. a preparation method of a fiber-graphene-thermoplastic polyarylether multi-scale composite material is characterized by comprising the following steps:
(1) Adding graphene oxide into a solvent N, N-dimethylacetamide, and performing ultrasonic dispersion for 1 ~ 2h to form a graphene oxide dispersion solution;
(2) Adding thermoplastic polyarylether resin into a solvent N, N-dimethylacetamide, and uniformly stirring to prepare a thermoplastic polyarylether resin solution with the mass concentration of 10 ~ 35%, wherein the thermoplastic polyarylether resin is selected from polyarylether ketone resin containing phenolphthalein side groups, polyarylether sulfone resin containing phenolphthalein side groups or polyarylether sulfone ketone resin containing phthalazinone biphenyl structures;
(3) Mixing the graphene oxide dispersion solution with a thermoplastic polyarylether resin solution, stirring for 1 ~ 2h, and then ultrasonically dispersing for 1 ~ 2h to prepare an impregnation solution, wherein the graphene oxide in the impregnation solution is 0.05 ~ 0.75.75% of the total mass of the polyarylether resin;
(4) Placing continuous fibers in an impregnation solution, fully impregnating the continuous fibers until the fibers in the continuous fibers are soaked, taking out the continuous fibers, drying the continuous fibers at 220 +/-10 ℃ for 2 ~ 3 hours, removing the solvent, and simultaneously carrying out in-situ thermal reduction on graphene oxide to obtain a graphene-containing prepreg;
(5) and (2) placing the prepreg containing the graphene into a mould, and preparing the fiber-graphene-thermoplastic polyarylether multi-scale composite material by compression molding or autoclave molding, wherein the temperature of 310 ~ 440 ℃, the pressure of 0.5 ~ 10MPa and the molding time of 3 ~ 4h are realized during compression molding or autoclave molding, and the particle size of the graphene in the fiber-graphene-thermoplastic polyarylether composite material is 5 ~ 400 nm.
2. The method for preparing the fiber-graphene-thermoplastic polyarylether multi-scale composite material according to claim 1, wherein the continuous fiber is selected from glass fiber, carbon fiber, aramid fiber or PBO fiber.
3. the method of claim 1, wherein the continuous fibers have a filament diameter of 2 ~ 18 μm, and wherein the continuous fibers are a graphene-thermoplastic polyarylether multi-scale composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710991858.2A CN107722595B (en) | 2017-10-23 | 2017-10-23 | Preparation method of fiber-graphene-thermoplastic polyarylether multi-scale composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710991858.2A CN107722595B (en) | 2017-10-23 | 2017-10-23 | Preparation method of fiber-graphene-thermoplastic polyarylether multi-scale composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107722595A CN107722595A (en) | 2018-02-23 |
| CN107722595B true CN107722595B (en) | 2019-12-17 |
Family
ID=61213087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710991858.2A Expired - Fee Related CN107722595B (en) | 2017-10-23 | 2017-10-23 | Preparation method of fiber-graphene-thermoplastic polyarylether multi-scale composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107722595B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109177207A (en) * | 2018-07-09 | 2019-01-11 | 黄河科技学院 | Para-aramid fiber enhances unsaturated-resin board making and stress measuring method |
| CN109142478B (en) * | 2018-08-30 | 2020-10-16 | 浙江大学 | High-molecular polymer film functionalized graphene modified electrode electrochemical sensor, and preparation method and application thereof |
| CN109233241B (en) * | 2018-09-25 | 2020-11-13 | 沈阳航空航天大学 | Graphene/polyarylethersulfone ketone conductive film and preparation method thereof |
| CN110323451B (en) * | 2019-04-28 | 2022-03-22 | 中国科学院山西煤炭化学研究所 | Multifunctional composite material based on graphene and polymer fibers and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199341A (en) * | 2011-04-07 | 2011-09-28 | 上海交通大学 | Preparation method of microwave absorbing material |
| CN102618014A (en) * | 2012-04-06 | 2012-08-01 | 沈阳航空航天大学 | Preparation method of phenolphthalein side group-containing polyarylether ketone (polyarylether sulphone) resin hybrid multi-scale composite material |
| CN102690426A (en) * | 2012-06-08 | 2012-09-26 | 浙江大学 | Method for preparing graphene/polymer composite material based on infrared irradiation |
| 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 |
| CN105368037A (en) * | 2015-11-30 | 2016-03-02 | 江门市优巨新材料有限公司 | Glass fiber-enhanced chain-extending modified polyether sulphone resin and preparation method therefor |
| CN106046747A (en) * | 2016-04-28 | 2016-10-26 | 电子科技大学 | A preparing technique for in-situ thermally-reduced poly(aryl ether nitrile)/graphene oxide heat-conducting composite film |
| CN106433084A (en) * | 2016-06-21 | 2017-02-22 | 江苏金陵特种涂料有限公司 | Graphene modified polyaryletherketone polymer material and preparation method thereof |
| CN106977882A (en) * | 2017-05-08 | 2017-07-25 | 北京化工大学 | A kind of heat-conductive composite material and preparation method thereof |
| CN107057273A (en) * | 2017-02-15 | 2017-08-18 | 山东圣泉新材料股份有限公司 | Phenol-formaldehyde resin modified, composite and its preparation method and application |
| CN107189354A (en) * | 2017-07-07 | 2017-09-22 | 齐鲁工业大学 | A kind of graphene nanometer sheet strengthens the preparation method of carbon fibre composite |
-
2017
- 2017-10-23 CN CN201710991858.2A patent/CN107722595B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199341A (en) * | 2011-04-07 | 2011-09-28 | 上海交通大学 | Preparation method of microwave absorbing material |
| CN102618014A (en) * | 2012-04-06 | 2012-08-01 | 沈阳航空航天大学 | Preparation method of phenolphthalein side group-containing polyarylether ketone (polyarylether sulphone) resin hybrid multi-scale composite material |
| CN102690426A (en) * | 2012-06-08 | 2012-09-26 | 浙江大学 | Method for preparing graphene/polymer composite material based on infrared irradiation |
| 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 |
| CN105368037A (en) * | 2015-11-30 | 2016-03-02 | 江门市优巨新材料有限公司 | Glass fiber-enhanced chain-extending modified polyether sulphone resin and preparation method therefor |
| CN106046747A (en) * | 2016-04-28 | 2016-10-26 | 电子科技大学 | A preparing technique for in-situ thermally-reduced poly(aryl ether nitrile)/graphene oxide heat-conducting composite film |
| CN106433084A (en) * | 2016-06-21 | 2017-02-22 | 江苏金陵特种涂料有限公司 | Graphene modified polyaryletherketone polymer material and preparation method thereof |
| CN107057273A (en) * | 2017-02-15 | 2017-08-18 | 山东圣泉新材料股份有限公司 | Phenol-formaldehyde resin modified, composite and its preparation method and application |
| CN106977882A (en) * | 2017-05-08 | 2017-07-25 | 北京化工大学 | A kind of heat-conductive composite material and preparation method thereof |
| CN107189354A (en) * | 2017-07-07 | 2017-09-22 | 齐鲁工业大学 | A kind of graphene nanometer sheet strengthens the preparation method of carbon fibre composite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107722595A (en) | 2018-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107722595B (en) | Preparation method of fiber-graphene-thermoplastic polyarylether multi-scale composite material | |
| CN101700705B (en) | Thermosetting resin glass fiber laminating composite material and preparation method thereof | |
| CN105152674A (en) | Preparation method of pantograph slide plate made of graphene modified carbon/carbon composite material | |
| CN113571725B (en) | Preparation process of graphite-based nanocomposite bipolar plate | |
| CN101831173A (en) | Bi-phthalonitrile resin glass fiber composite material toughened by poly(arylene ether nitrile) and preparation method thereof | |
| CN110396280B (en) | Fiber-reinforced epoxy resin-based composite material and preparation method thereof | |
| CN109251518A (en) | A kind of high-performance carbon fibre/graphene nylon 6 composite material preparation method | |
| CN102796373A (en) | Graphene/cyanate ester/bimaleimide composite material and preparation method thereof | |
| CN110181917B (en) | Hybrid film modified carbon fiber composite material and preparation method thereof | |
| CN110713612B (en) | Low-temperature-resistant circulating composite material and preparation method thereof | |
| CN102199265B (en) | Long carbon chain nylon modified phenolic resin and preparation method thereof | |
| CN110983759A (en) | Graphene modified carbon fiber pre-vulcanized fiber fabric and preparation method thereof | |
| CN111073222A (en) | Preparation method of graphene oxide/carbon nanotube reinforced glass fiber laminated plate | |
| CN112724601B (en) | Carbon fiber reinforced composite material with high interface strength and strong interface conductivity and preparation method thereof | |
| CN116215028B (en) | Environment-friendly composite board based on recycled fibers and manufacturing process thereof | |
| CN110527129B (en) | Polyether-ether-ketone porous foam material and preparation method thereof | |
| CN110894338B (en) | Controllable deformation accurate regulation and control composite material based on super-elastic network and preparation method and application thereof | |
| CN111320841A (en) | Aramid fiber/carbon nanotube composite reinforced carbon fiber resin prepreg | |
| CN109161188A (en) | A kind of high-performance glass fiber/graphene nylon 6 composite material preparation method | |
| CN115716748A (en) | Graphite tube modified by resin glassy carbon | |
| CN113650388B (en) | Z-direction high-heat-conductivity epoxy resin-based continuous fiber reinforced composite material laminated board | |
| CN102329431B (en) | Preparation method of epoxy resin composite material strengthened by in situ growth of CNT (carbon nano tube) on surface of quartz fibre | |
| CN103289079B (en) | Composite material of nylon 6/aramid fibres and preparation method for same | |
| CN101565535A (en) | Heat resistant epoxide resin and preparation method thereof | |
| CN113801431A (en) | High-toughness high-strength phenolic resin material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191217 Termination date: 20201023 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |