CN111187506A - Method for preparing composite material from graphene nano paste - Google Patents
Method for preparing composite material from graphene nano paste Download PDFInfo
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- CN111187506A CN111187506A CN202010042250.7A CN202010042250A CN111187506A CN 111187506 A CN111187506 A CN 111187506A CN 202010042250 A CN202010042250 A CN 202010042250A CN 111187506 A CN111187506 A CN 111187506A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
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- 238000000034 method Methods 0.000 title claims abstract description 43
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- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 claims description 2
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- 230000008023 solidification Effects 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
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- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
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- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 2
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- PQOBAICDGYSPLH-UHFFFAOYSA-N 4,5-dimethylimidazol-2-one Chemical compound CC1=NC(=O)N=C1C PQOBAICDGYSPLH-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- 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
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
The invention discloses a method for preparing a composite material by using graphene paste. The method comprises the steps of adding original graphite into low-concentration polymer dispersion liquid, adopting a liquid phase stripping technology, taking polymer macromolecules as a dispersing agent, successfully preparing graphene nano paste (20-200mg/ml), and preparing the graphene/polymer nano composite material with excellent performance by blade coating, evaporation, spraying and other methods. The graphene nano paste prepared by the method has the advantages of high dispersion, high concentration, high stability and the like, and the graphene-based composite material prepared by molding and drying has the advantages of uniform dispersion of graphene, simple preparation process and the like, so that a new thought and technical scheme are provided for the preparation of the graphene-based composite material.
Description
Technical Field
The invention relates to the technical field of preparation of composite materials, in particular to a method for preparing a composite material from graphene nano paste.
Background
The polymer has the advantages of low mass density, corrosion resistance, excellent processability, low cost and the like, so that the polymer is widely applied to a plurality of fields. However, the polymer lacks functionality, and in some fields where functionality is required, the use of the polymer is limited. Therefore, the polymer is modified by adopting the filler with excellent characteristics of high heat conductivity, high electric conductivity and the like, and the method is an effective way for widening the application field of the polymer. The graphene has excellent mechanical property, thermal conductivity, electrical property and the like, and can be used as a nano filler to be added into a polymer matrix to effectively improve various properties of the polymer, so that the graphene and the nano filler are used as raw materials to prepare the composite material, and the composite material not only has excellent functionality, but also can keep certain excellent characteristics of the polymer.
Currently, the liquid phase stripping method is an effective method for preparing graphene dispersion liquid, and comprises ultrasonic stripping, a chemical intercalation stripping method, ball milling stripping, high-pressure spraying, high-speed shearing and the like, so that the method is a method for continuously producing the graphene dispersion liquid on a large scale. For example, Coleman et al, san Sanyi university of Dublin, Ireland, first prepared graphene in a N-methylpyrrolidone (NMP) solvent using the ultrasonic exfoliation method at concentrations of 0.01mg/mL (Nat Nanotechnol 2008,3(9), 563-568). Green et al, Dezhou university of technology, USA, utilizes ultrasonic exfoliation technology to take expanded graphite as raw material, and exfoliation concentration in ionic liquid is as high as 5.8mg/mL (Carbon 2019,142,261 and 268). Tengtangchao et al prepared the macro graphene dispersion with a concentration of 2.6mg/mL in a large scale by a large and small sphere compounding technique (Adv Funct Mater 2017,27(20), 1700240). Although the current liquid phase stripping technology can prepare high-quality graphene, the method still has the defects of low concentration, incapability of realizing large-scale production and the like, and limits the practical application of the high-content and high-thermal-conductivity nanocomposite. Based on the method, the method for preparing the graphene nano paste by using the graphene nano paste has important significance, is high in dispersity, high in stability and continuous, and can be used for continuous large-area production. Meanwhile, the preparation of the graphene/high polymer material nano paste by the one-step method is beneficial to the preparation of a high-performance composite material, has the characteristics of simple steps, uniform dispersion of graphene and the like, and is obviously different from the preparation of the current graphene composite material.
Disclosure of Invention
The invention mainly aims to provide a graphene nano paste with ultrahigh concentration, high yield and high stable dispersion and a preparation method of a composite material thereof, so as to overcome the problems of low concentration, low yield and poor stability of a graphene dispersion liquid prepared by the prior art and the problems of complicated steps and poor dispersibility of the composite material prepared by the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme: a method for preparing a composite material by using graphene nano paste comprises the following specific steps:
(1) dispersing a polymer with the solid content of 0-45% into a solvent to obtain a low-concentration polymer dispersion liquid, carrying out ultrasonic treatment for 0-30min, and carrying out stirring treatment for 1-3h at the stirring speed of 100-2000 r/min;
(2) adding graphite powder into the low-concentration polymer dispersion liquid obtained in the step (1), performing ultrasonic treatment for 30-1 h, and stirring for 12-200 h at a stirring speed of 200-4000 r/min;
(3) in the step (2), successfully preparing the high-concentration graphene nano paste through liquid phase stripping, wherein the concentration of the finally prepared graphene/polymer nano paste is 20-100 mg/ml;
(4) and (3) directly putting the graphene/polymer nano paste prepared in the step (3) into use according to requirements, or preparing graphene/polymer composite materials with different shapes and functionality by adopting different subsequent processes.
Preferably, the polymer is one or more of polyamide, polyaluminum chloride, polyacrylic acid, polyacrylamide, polyacrylonitrile, polyarylate, polycarbonate, tetrafluoroethylene, polyethylene, polydiallyl isophthalate, phenol resin, polyethylene glycol, propylene glycol, polypropylene, polyisoprene, polyisobutylene, polystyrene, polyvinyl chloride, polyoxymethylene, polyphenylene oxide, polyurethane, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinylidene fluoride, natural rubber, nitrile rubber, and the like.
Preferably, the solvent of the polymer dispersion is one or more selected from N-methylpyrrolidone, vinylpyrrolidone, N-dodecylpyrrolidone, water, methanol, ethanol, dimethyl phthalate, ethanol, acetone, vinyl acetate, dimethyl sulfoxide, dichlorobenzene, chloroform, tetrahydrofuran, N-octylpyrrolidone, cyclohexylpyrrolidone, dimethylimidazolone, N-methylformamide, dimethylformamide, cyclohexane, benzyl benzoate (meth) acrylate, isopropanol, N-butyl acrylate, ethylene glycol, toluene, heptane, pentane, hexane, formamide, and dimethylformamide.
Preferably, the graphene nano paste prepared composite material comprises the following components in parts by weight: graphene (2-20 wt%), polymer (0-45 wt%), and solvent in balance.
Preferably, the graphene is prepared by liquid phase exfoliation of raw graphite, expanded graphite, expandable graphite, or the like.
Preferably, the graphite mechanically exfoliated in the liquid phase has a thickness of 20 layers or less, and the graphene nanoplatelets have an average size of about 600 nm.
Preferably, the subsequent process is one or more of a blade coating method, a dropping coating method, a spin coating method, evaporation or drying, cooling or solidification, coating, calcination, compression molding, injection molding, spray coating, vacuum filtration, irradiation, filtration, thermal evaporation, inkjet printing, screen printing, gravure printing, electrostatic spinning, electrodeposition, interfacial deposition, and the like.
Preferably, the graphene/polymer composite materials with different shapes are prepared from one or more of films, plates, pipes, bars, sheets, profiles, filamentous materials and the like.
Preferably, the graphene/polymer composite material has excellent functionality as follows: mechanical property, heat-conducting property, electric conductivity, electromagnetic shielding, optical property, biocompatibility, adsorption property, catalytic property, barrier property, wave-absorbing property, friction resistance, corrosion resistance, high light transmittance, high electron migration, high surface area and the like.
The graphene/polymer nano paste prepared by the method has the characteristics of ultrahigh concentration, high dispersion, high stability and the like, is simple in operation process, can be prepared in one step, reduces the using amount of a solvent, reduces the cost, is convenient to transport, and promotes the practical application of the graphene/polymer composite material.
Drawings
Fig. 1 is an optical photograph of the graphene nanopaste obtained in example.
Fig. 2 is a scanning electron micrograph of the graphene nanoplatelets obtained in example 1.
Fig. 3 is a transmission electron micrograph of the graphene nanoplatelets obtained in example 1.
Fig. 4 is a transmission electron microscope high-resolution photograph of the graphene nanoplatelets obtained in example 1.
Fig. 5 is an optical photograph of the graphene/polymer nanocomposite film obtained in example 1.
Detailed Description
Example 1
(1) Adding thermoplastic polyurethane elastomer rubber (TPU) with the solid content of 1 wt% into 300mL of N-methylpyrrolidone solution, carrying out ultrasonic treatment for 20min, and stirring for 2h at 1500r/min to fully disperse the TPU to obtain a low-concentration TPU dispersion liquid.
(2) Adding 12g of original graphite into the dispersion liquid in the step (1), performing ultrasonic treatment for 30min, and stirring at 3000r/min for 48h to prepare the graphene nano paste with few layers and high concentration, wherein the graphene nano paste is shown in figure 1.
(3) And (3) diluting the graphene nanopaste in the step (2), and characterizing by using a scanning electron microscope and a transmission electron microscope, which shows that the few-layer graphene nanoplatelets (SEG) are successfully prepared, as shown in FIGS. 2 and 3. FIG. 4 shows that the number of graphene nanoplatelets is 3-10, which indicates that the few-layered graphene nanoplatelets are successfully prepared.
(4) In the step (2), a liquid phase stripping technology is adopted, and TPU macromolecules are used as a dispersing agent to successfully prepare the high-concentration SEG/TPU nano paste with the concentration of 40 mg/ml.
(5) And (3) preparing the SEG/TPU nano paste in the step (4) into the SEG/TPU nano composite film with excellent performance by using methods such as blade coating, evaporation and the like, as shown in figure 5.
The SEG/TPU nano composite film preparation process method comprises one or more of blade coating method, evaporation or drying, dripping method, spin coating method, coating, compression molding, injection molding, spraying, vacuum filtration, thermal evaporation method, ink-jet printing method, electrodeposition method and the like.
The SEG/TPU nano composite film has the following excellent properties: mechanical property, heat-conducting property, electric conductivity, electromagnetic shielding, optical property, biocompatibility, adsorption property, catalytic property, barrier property, wave-absorbing property, friction resistance, corrosion resistance, high light transmittance, high electron migration, high surface area and the like.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto. Those skilled in the art, having the benefit of this disclosure, will appreciate that other modifications and variations can be made without departing from the scope of the invention as defined by the appended claims.
Example 2
(1) Adding thermoplastic polyurethane elastomer rubber (TPU) with the solid content of 2 wt% into 300mL of N-methylpyrrolidone solution, carrying out ultrasonic treatment for 20min, and stirring for 2h at 1500r/min to fully disperse the TPU to obtain a low-concentration TPU dispersion liquid.
(2) Adding 12g of expanded graphite into the dispersion liquid in the step (1), performing ultrasonic treatment for 30min, and stirring at 3000r/min for 72h to prepare the graphene nano paste with few layers and high concentration, wherein the graphene nano paste is shown in figure 1.
(3) And (3) diluting the graphene nanopaste in the step (2), and characterizing by using a scanning electron microscope and a transmission electron microscope, which shows that the few-layer graphene nanoplatelets (SEG) are successfully prepared, as shown in FIGS. 2 and 3. FIG. 4 shows that the number of graphene nanoplatelets is 3-10, which indicates that the few-layered graphene nanoplatelets are successfully prepared.
(4) In the step (2), a liquid phase stripping technology is adopted, and TPU macromolecules are used as a dispersing agent to successfully prepare the high-concentration SEG/TPU nano paste with the concentration of 40 mg/ml.
(5) And (3) preparing the SEG/TPU nano paste in the step (4) into the SEG/TPU nano composite film with excellent performance by using methods such as blade coating, evaporation and the like, as shown in figure 5.
The SEG/TPU nano composite film preparation process method comprises one or more of blade coating method, evaporation or drying, dripping method, spin coating method, coating, compression molding, injection molding, spraying, vacuum filtration, thermal evaporation method, ink-jet printing method, electrodeposition method and the like.
The SEG/TPU nano composite film has the following excellent properties: mechanical property, heat-conducting property, electric conductivity, electromagnetic shielding, optical property, biocompatibility, adsorption property, catalytic property, barrier property, wave-absorbing property, friction resistance, corrosion resistance, high light transmittance, high electron migration, high surface area and the like.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto. Those skilled in the art, having the benefit of this disclosure, will appreciate that other modifications and variations can be made without departing from the scope of the invention as defined by the appended claims.
Claims (9)
1. A method for preparing a composite material by using graphene nano paste is characterized by comprising the following steps:
(1) dispersing a polymer with the solid content of 0-45 wt% into a solvent to obtain a low-concentration polymer dispersion liquid, carrying out ultrasonic treatment for 0-30min, and carrying out stirring treatment for 1-3h at the stirring speed of 100-2000 r/min;
(2) adding graphite powder into the low-concentration polymer dispersion liquid obtained in the step (1), performing ultrasonic treatment for 30-1 h, and stirring for 12-200 h at a stirring speed of 200-4000 r/min;
(3) in the step (2), successfully preparing the high-concentration graphene nano paste through liquid phase stripping, wherein the concentration of the finally prepared graphene/polymer nano paste is 20-200 mg/ml;
(4) and (3) directly putting the graphene/polymer nano paste prepared in the step (3) into use according to requirements, or preparing graphene/polymer composite materials with different shapes and functionality by adopting different subsequent processes.
2. The graphene nanopaste prepared composite material according to claim 1, wherein in the step (1), the polymer is one or more of polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polyarylate, polycarbonate, tetrafluoroethylene, polyethylene, polydiallyl isophthalate, phenolic resin, polyethylene glycol, propylene glycol, polypropylene, polyisoprene, polyisobutylene, polystyrene, polyvinyl chloride, polyoxymethylene, polyphenylene oxide, polyurethane, polyvinyl alcohol, polyvinyl pyrrolidone, polyaluminum chloride, polyvinylidene fluoride, natural rubber, nitrile rubber, and the like.
3. The graphene nanopaste-prepared composite material according to claim 1, wherein in the step (1), the solvent of the polymer dispersion is one or more selected from N-methylpyrrolidone, vinylpyrrolidone, N-dodecylpyrrolidone, water, methanol, ethanol, dimethyl phthalate, ethanol, acetone, vinyl acetate, dimethyl sulfoxide, dichlorobenzene, chloroform, tetrahydrofuran, N-octylpyrrolidone, cyclohexylpyrrolidone, dimethylimidazolidone, N-methylformamide, dimethylformamide, cyclohexane, benzyl (meth) benzoate, isopropanol, N-butyl acrylate, ethylene glycol, toluene, heptane, pentane, hexane, formamide, dimethylformamide and the like.
4. The graphene nanopaste-prepared composite material according to claim 1, which comprises the following components in parts by weight: graphene (2-20 wt%), polymer (0-45 wt%), and solvent in balance.
5. The graphene nanopaste-prepared composite material according to claim 4, wherein the graphene is prepared by liquid phase exfoliation using raw graphite, expanded graphite, expandable graphite, or the like.
6. The graphene nanopaste-prepared composite material according to claim 4 or 5, wherein the liquid-phase mechanically exfoliated graphite has a thickness of 20 layers or less and the average size of the graphene nanoplatelets is around 600 nm.
7. The graphene nanopaste-prepared composite material according to claim 1, wherein in the step (4), the subsequent process is one or more of blade coating, dropping coating, spin coating, evaporation or drying, cooling or solidification, curing, coating, calcining, compression molding, injection molding, spray coating, vacuum filtration, irradiation, filtration, thermal evaporation, inkjet printing, screen printing, gravure printing, electrostatic spinning, electrodeposition, interfacial deposition, and the like.
8. The graphene nanopaste composite material according to claim 1, wherein in the step (4), the graphene/polymer composite material with different shapes is one or more of a film, a plate, a pipe, a bar, a sheet, a profile, a filamentous material and the like.
9. The liquid phase exfoliation method for preparing highly dispersed graphene/polymer nanopaste according to claim 1, wherein in the step (4), the graphene/polymer composite material has excellent functionality as follows: mechanical property, heat-conducting property, electric conductivity, electromagnetic shielding, optical property, biocompatibility, adsorption property, catalytic property, barrier property, wave-absorbing property, friction resistance, corrosion resistance, high light transmittance, high electron migration, high surface area and the like.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103254455A (en) * | 2013-04-23 | 2013-08-21 | 中国科学院上海光学精密机械研究所 | Preparation method of graphene-thickening polymer composite film |
TW201441148A (en) * | 2013-04-26 | 2014-11-01 | Univ Nat Sun Yat Sen | Method for forming a large-area graphene layer on a porous substrate |
CN106517171A (en) * | 2015-09-10 | 2017-03-22 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphene aerogel |
CN107522961A (en) * | 2017-03-30 | 2017-12-29 | 上海大学 | Polystyrene-based high-heat-conductive composite material and preparation method thereof |
CN108819400A (en) * | 2018-06-26 | 2018-11-16 | 青岛科技大学 | A method of anisotropic thermal block materials are prepared using Gibbs free energy induction |
EP3770207A1 (en) * | 2018-03-23 | 2021-01-27 | Avanzare Innovacion Tencologica S.L. | Use of high-aspect-ratio graphene materials as additives for thermoplastic materials |
-
2020
- 2020-01-15 CN CN202010042250.7A patent/CN111187506B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103254455A (en) * | 2013-04-23 | 2013-08-21 | 中国科学院上海光学精密机械研究所 | Preparation method of graphene-thickening polymer composite film |
TW201441148A (en) * | 2013-04-26 | 2014-11-01 | Univ Nat Sun Yat Sen | Method for forming a large-area graphene layer on a porous substrate |
CN106517171A (en) * | 2015-09-10 | 2017-03-22 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphene aerogel |
CN107522961A (en) * | 2017-03-30 | 2017-12-29 | 上海大学 | Polystyrene-based high-heat-conductive composite material and preparation method thereof |
EP3770207A1 (en) * | 2018-03-23 | 2021-01-27 | Avanzare Innovacion Tencologica S.L. | Use of high-aspect-ratio graphene materials as additives for thermoplastic materials |
CN108819400A (en) * | 2018-06-26 | 2018-11-16 | 青岛科技大学 | A method of anisotropic thermal block materials are prepared using Gibbs free energy induction |
Non-Patent Citations (7)
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113683858A (en) * | 2021-07-13 | 2021-11-23 | 浙江工业大学 | Preparation method of conductive 3D printing graphene composite material with high mechanical strength |
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