CN111777841B - Lamellar anisotropy-based graphene/epoxy resin composite material and preparation method thereof - Google Patents
Lamellar anisotropy-based graphene/epoxy resin composite material and preparation method thereof Download PDFInfo
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
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- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
Abstract
The invention relates to a lamellar anisotropy-based graphene/epoxy resin composite material and a preparation method thereof, wherein graphene aerogel is obtained by performing steps of bidirectional freezing, imidization, graphitization and the like on a mixed solution of graphene oxide and polyamic acid salt, and the epoxy composite material is obtained by performing controllable compression on the graphene aerogel and then compounding and curing the graphene aerogel and epoxy resin. The graphene/epoxy resin composite material has high thermal conductivity in the graphene orientation direction, and the shell-like brick mud structure on the microcosmic surface endows the composite material with high fracture toughness. The controllable compression of the aerogel solves the problem that the filling content cannot be increased when the graphene aerogel is used as a heat-conducting filler; the lamellar structure constructed by the bidirectional freezing method solves the problem that the toughness of the composite material is reduced when the filler content is too high.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a graphene/epoxy resin composite material based on lamellar anisotropy and a preparation method thereof.
Background
With the rapid development of electronic devices, heat dissipation management thereof becomes a great challenge which must be faced to affect the use safety and service life of microelectronic devices. Although the polymer material has the characteristics of light weight, easy processing, chemical corrosion resistance, low cost and the like, the polymer material has lower thermal conductivity (less than 0.5W m) -1 K -1 ) Obviously, it is not enough to meet the demand, so there is an urgent need to develop a polymer composite material with excellent thermal conductivity to meet the demand of industrial development.
Filling a filler with high thermal conductivity into a polymer matrix is an efficient method for obtaining a high thermal conductive polymer composite. For example, a polymer matrix is filled with a metal filler such as silver, copper, aluminum and the like, a ceramic filler such as alumina, aluminum nitride, boron nitride, silicon carbide and the like, and a carbon material such as carbon black, carbon nanotubes, graphene and the like to prepare the heat-conducting composite material. However, conventional metallic and ceramic fillers have limited reinforcing effects and require higher loadings to achieve higher thermal conductivity. The carbon material has the characteristics of excellent thermal conductivity and light weight, so that the carbon filler becomes a filler which has the greatest development prospect in preparing high-thermal-conductivity composite materials. In the commonly used carbon fillers, graphene has attracted much attention because of its excellent mechanical properties, high thermal conductivity and high electrical conductivity.
At present, the thermal conductivity of the graphene/polymer heat-conducting composite material is mainly improved by adopting the following methods: (1) the quality of the graphene is improved, and the high-quality graphene can effectively reduce phonon scattering so as to ensure that the graphene has high thermal conductivity; (2) a three-dimensional heat conduction passage is constructed, and the construction of the heat conduction passage can effectively reduce the thermal contact resistance between graphene sheets, so that the heat conductivity of the composite material is improved; (3) the graphene is oriented, and the in-plane thermal conductivity of the graphene is higher than that of the graphene in the vertical direction, so that the thermal conductivity of the composite material in the direction can be effectively improved by orienting the graphene in the in-plane direction; (4) researches show that the thermal conductivity of the composite material is increased along with the increase of the heat-conducting filler, so that the thermal conductivity of the composite material can be effectively improved by increasing the filling content of the graphene. However, the thermal conductivity of the graphene/polymer heat-conducting composite material at present has a great difference from the theoretical thermal conductivity enhancement, and a great promotion space is provided. And the processing performance of the high polymer material is reduced when the graphene content is higher, and the higher filler content can cause the density of the composite material to be increased and the toughness to be reduced, so that the original advantages of the high polymer material are lost.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a graphene/epoxy resin composite material based on lamellar anisotropy and a preparation method thereof. In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: the utility model provides a graphite alkene/epoxy resin combined material based on lamellar anisotropy, obtains after carrying out controllable compression and epoxy resin complex solidification to graphite alkene aerogel, combined material have the "brick mud" structure of imitative shell.
The invention also protects the preparation method of the graphene/epoxy resin composite material, and the lamellar anisotropic graphene aerogel is a lamellar anisotropic high-quality graphene aerogel obtained by performing the steps of bidirectional freezing, imidization, graphitization and the like on the mixed solution of graphene oxide and polyamic acid salt; the graphene/epoxy resin composite material is obtained by controllably compressing graphene aerogel and then compounding and curing the graphene/epoxy resin aerogel with epoxy resin.
According to the preparation method, a graphene aerogel laminated structure is endowed through a bidirectional freezing technology, the quality of graphene is improved through high-temperature heat treatment, the filling content of graphene in the composite material is improved through controllable compression of aerogel, the obtained graphene/epoxy resin composite material has high thermal conductivity and high fracture toughness, and the problem that the mechanical property of a high-molecular composite material is reduced when the filling content is high is solved. The composite material has a shell-like brick mud structure, has high thermal conductivity and high fracture toughness.
In a preferred embodiment of the present invention, the preparation method comprises the steps of:
(1) preparing Graphene Oxide (GO) and water-soluble polyamic acid salt (PAAS);
(2) preparation of anisotropic high-quality graphene aerogel having a layered structure: mixing Graphene Oxide (GO) with water-soluble polyamic acid salt (PAAS) to obtain GO/PAAS suspension, and preparing anisotropic high-quality graphene aerogel with a laminated structure through steps of bidirectional freezing, freeze drying, imidization treatment and high-temperature graphitization treatment;
(3) preparing a graphene/epoxy resin composite material: and (3) compounding the aerogel obtained in the step (2) with an epoxy resin precursor by adopting a vacuum auxiliary impregnation method, compressing the aerogel and the epoxy resin precursor, and heating and curing the compressed aerogel to obtain the graphene/epoxy resin composite material.
In a preferred embodiment of the invention, in the step (1), a modified Hummers method is adopted to prepare graphite oxide, and the graphite oxide is subjected to ultrasonic treatment to prepare graphene oxide; the water-soluble polyamic acid salt is prepared by synthesizing polyamic acid by adopting a condensation polymerization method and then dissolving the polyamic acid in aqueous solution of triethylamine.
In a preferred embodiment of the present invention, in step (1), the Hummers method is: adding potassium permanganate into a mixture of concentrated sulfuric acid, flake graphite and sodium nitrate, carrying out acid washing and water washing after oxidation reaction, and centrifuging to be neutral to obtain graphite oxide.
In a preferred embodiment of the present invention, in step (1), the duration of the ultrasonic treatment is 1 to 30 min, preferably 10 to 20 min.
In a preferred embodiment of the present invention, in the step (1), the condensation polymerization method is: under the protection of nitrogen, pyromellitic anhydride is added into N-N dimethylacetamide solution of 4, 4' -diaminodiphenyl ether, and after the reaction is finished under the ice bath condition, the product is washed by water, filtered and dried in vacuum to obtain polyamic acid.
In a preferred embodiment of the present invention, in step (1), the mass ratio of triethylamine to polyamic acid is (0.4-0.6):1, preferably (0.48-0.52): 1.
In a preferred embodiment of the invention, in step (2), the total concentration of the mixed suspension of GO and PAAS is between 20 and 60 mg/ml, preferably 40 mg/ml.
In a preferred embodiment of the present invention, in the step (2), the mass ratio of GO to PAAS is 3: 7. 4: 6. 5: 5, preferably 4: 6; the imidization treatment temperature is 200- o C, preferably 300 o C; graphitization temperature is 2800 o C, the reaction time is 60-180 min, preferably 120 min; all reactions were carried out under argon.
In the preferred embodiment of the present invention, in step (3), the epoxy resin monomer, the diluent, the curing agent, and the accelerator are uniformly mixed according to a certain proportion, the obtained aerogel is immersed in the mixture, the aerogel is taken out under vacuum conditions and compressed to different degrees, and finally the composite material is prepared by heating and curing.
In a preferred embodiment of the invention, in the step (3), the mass ratio of the epoxy resin monomer, the diluent, the curing agent and the accelerator is 8:2:9.48: 0.0576; the diluent is ethylene glycol diglycidyl ether, the curing agent is methyl hexahydrophthalic anhydride, and the accelerator is 2,4, 6-tri (dimethylaminomethyl) phenol.
In a preferred embodiment of the present invention, in step (3), the compression direction for the aerogel is the direction perpendicular to the orientation direction of the lamellar structure; a degree of compression of 30% to 70%, preferably 70%; the curing temperature is 80-120 DEG C o And C, the reaction time is 2-4 h.
The invention also protects the graphene/epoxy resin composite material which is prepared by the method and is based on the anisotropic high-quality graphene aerogel and has high heat conductivity and high toughness.
Compared with the prior art, the invention has the excellent effects that:
1) according to the invention, by adopting a bidirectional freezing technology and regulating the ratio of GO to PAAS and reaction parameters in the preparation process, the anisotropic sheet-layered high-quality graphene three-dimensional heat-conducting network with compact and regular orientation can be finally obtained, so that the interface thermal resistance is reduced, and the thermal conductivity of the composite material is further improved.
2) According to the invention, the filling content of graphene in the composite material is increased through controllable compression of the graphene aerogel, so that the thermal conductivity of the composite material is increased, the problem that the filling content cannot be increased when the graphene aerogel is used as a heat-conducting filler is solved, and the uniform dispersion of the filler in a matrix can be fully ensured.
3) After the composite material is compounded with epoxy resin, the lamellar graphene three-dimensional aerogel enables the composite material to have the structural characteristic of 'brick mud' similar to shells, so that the composite material is endowed with high fracture toughness, and the problem of toughness reduction of the composite material when the filler content is too high is solved to a certain extent.
Drawings
The invention is further illustrated with reference to the accompanying drawings:
FIG. 1 is a schematic diagram of the preparation process of the present invention;
2-3 are SEM images of the obtained anisotropic high-quality graphene aerogel with a layered structure in different directions;
fig. 4 is an SEM image of the prepared graphene/epoxy composite material;
FIG. 5 is a graph comparing thermal conductivity of different composites;
fig. 6 is a graph comparing fracture toughness of the obtained graphene/epoxy composite material and epoxy resin.
Detailed Description
The process of the present invention is illustrated below by way of specific examples, but the invention is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1: uniformly mixing 12 ml of PAAS solution with the concentration of 80 mg/ml, 21.5 ml of GO suspension with the concentration of 29.8 ml and 6.5 ml of water, and stirring for 2 hours after carrying out ultrasonic treatment for 15 min to obtain a mixed suspension. And pouring the mixed suspension into a PTFE (polytetrafluoroethylene) mold for bidirectional freezing, and after the mixed suspension is completely frozen, carrying out freeze drying for 72 hours to obtain the PAAS/GO mixed aerogel. Placing it under the protection of argon gas 300 o C imidization treatment for 4 h, and then 2800 under the protection of argon o And C, performing graphitization treatment for 2 h to obtain the anisotropic high-quality graphene aerogel with a layered structure. Uniformly mixing an epoxy monomer, a diluent, a curing agent and an accelerator according to a ratio, immersing the graphene aerogel, keeping the graphene aerogel for 12 hours under a vacuum condition, taking out the graphene aerogel, and keeping the graphene aerogel for 0.5 mm min along a direction perpendicular to a sheet layer -1 Is compressed by 70%, then 80% o C reaction for 4 h, 120 o And C, reacting for 2 hours to obtain the composite material, and carrying out heat conductivity test and notch sample three-point bending test on the composite material.
FIG. 1 is a schematic view of the production process of the present invention; fig. 2 is an SEM image of the graphene aerogel in a direction parallel to the orientation direction, and fig. 3 is an SEM image of the graphene aerogel in a direction perpendicular to the orientation direction, and it can be seen that the graphene aerogel prepared by the two-way freezing method has a regular and dense sheet orientation. After being compounded with epoxy resin, as can be seen from fig. 4, the epoxy resin is densely filled and tightly combined with graphene, and the composite material has a structure similar to that of "brick mud" of shells. FIG. 5 is a comparison of thermal conductivity of graphene/epoxy resin composite material in the direction of sheet orientation, and it can be seen that the thermal conductivity of the composite material prepared by the invention can reach 20W m -1 K -1 And has high thermal conductivity. Fig. 6 is a graph comparing fracture toughness of the epoxy resin and the composite material, and it can be seen from the graph that the fracture of the epoxy resin is brittle fracture, and after the epoxy resin is compounded with the lamellar high-quality graphene, the fracture toughness of the composite material is obviously improved.
Example 2: 12 ml PAAS solution at 80 mg/ml, 21.5 ml GO suspension at 29.8 ml, 6.5 ml water were mixedMixing uniformly, performing ultrasonic treatment for 15 min, and stirring for 2 h to obtain a mixed suspension. And pouring the mixed suspension into a PTFE (polytetrafluoroethylene) mold for bidirectional freezing, and after the mixed suspension is completely frozen, carrying out freeze drying for 72 hours to obtain the PAAS/GO mixed aerogel. Placing it under the protection of argon gas 300 o C imidizing for 4 h, and then 2800 under the protection of argon o And C, performing graphitization treatment for 2 h to obtain the anisotropic high-quality graphene aerogel with a layered structure. Uniformly mixing an epoxy monomer, a diluent, a curing agent and an accelerator according to a ratio, immersing the graphene aerogel, keeping the mixture for 12 hours under a vacuum condition, taking out the mixture, and keeping the mixture for 0.5 mm min along a direction perpendicular to a lamellar layer -1 Is compressed by 50% and then 80% of o C reacting for 4 h, 120 o And C, reacting for 2 h to obtain the composite material, and carrying out heat conductivity test and notch sample three-point bending test on the composite material.
Example 3: uniformly mixing 12 ml of PAAS solution with the concentration of 80 mg/ml, 21.5 ml of GO suspension with the concentration of 29.8 ml and 6.5 ml of water, and stirring for 2 hours after carrying out ultrasonic treatment for 15 min to obtain a mixed suspension. And pouring the mixed suspension into a PTFE (polytetrafluoroethylene) mold for bidirectional freezing, and after the mixed suspension is completely frozen, carrying out freeze drying for 72 hours to obtain the PAAS/GO mixed aerogel. Placing it under the protection of argon gas 300 o C imidizing for 4 h, and then 2800 under the protection of argon o And C, performing graphitization treatment for 2 h to obtain the anisotropic high-quality graphene aerogel with a layered structure. Uniformly mixing an epoxy monomer, a diluent, a curing agent and an accelerator according to a ratio, immersing the graphene aerogel, keeping the graphene aerogel for 12 hours under a vacuum condition, taking out the graphene aerogel, and keeping the graphene aerogel for 0.5 mm min along a direction perpendicular to a sheet layer -1 Is compressed by 30% and then 80% of o C reacting for 4 h, 120 o And C, reacting for 2 hours to obtain the composite material, and carrying out heat conductivity test and notch sample three-point bending test on the composite material.
Example 4: 12 ml of PAAS solution with the concentration of 80 mg/ml, 21.5 ml of GO suspension with the concentration of 29.8 ml and 6.5 ml of water are uniformly mixed, and the mixture is stirred for 2 hours after being subjected to ultrasonic treatment for 15 min to obtain mixed suspension. And pouring the mixed suspension into a PTFE (polytetrafluoroethylene) mold for bidirectional freezing, and after the mixed suspension is completely frozen, carrying out freeze drying for 72 hours to obtain the PAAS/GO mixed aerogel. Placing it under the protection of argon gas 300 o C imidization treatment for 4 h, and then 2800 under the protection of argon o And C, performing graphitization treatment for 2 h to obtain the anisotropic high-quality graphene aerogel with a layered structure. Uniformly mixing an epoxy monomer, a diluent, a curing agent and an accelerator according to a ratio, immersing the graphene aerogel, keeping the graphene aerogel under a vacuum condition for 12 hours, taking out the graphene aerogel, and then 80 percent mixing o C reacting for 4 h, 120 o And C, reacting for 2 h to obtain the composite material, and carrying out heat conductivity test and notch sample three-point bending test on the composite material.
Example 5: 14 ml of PAAS solution with the concentration of 80 mg/ml, 16.1 ml of GO suspension with the concentration of 29.8 ml and 9.9 ml of water are mixed uniformly, and the mixture is stirred for 2 hours after being subjected to ultrasonic treatment for 15 min to obtain mixed suspension. And pouring the mixed suspension into a PTFE (polytetrafluoroethylene) mold for bidirectional freezing, and after the mixed suspension is completely frozen, carrying out freeze drying for 72 hours to obtain the PAAS/GO mixed aerogel. Placing it under the protection of argon gas 300 o C imidizing for 4 h, and then 2800 under the protection of argon o And C, performing graphitization treatment for 2 h to obtain the anisotropic high-quality graphene aerogel with a layered structure. Uniformly mixing an epoxy monomer, a diluent, a curing agent and an accelerator according to a ratio, immersing the graphene aerogel, keeping the graphene aerogel under a vacuum condition for 12 hours, taking out the graphene aerogel, and then 80 percent mixing o C reaction for 4 h, 120 o And C, reacting for 2 hours to obtain the composite material, and testing the heat conductivity of the composite material.
Example 6: 10 ml of PAAS solution with the concentration of 80 mg/ml, 26.8 ml of GO suspension with the concentration of 29.8 ml and 3.2 ml of water are mixed evenly, and the mixture is stirred for 2 hours after being subjected to ultrasonic treatment for 15 min to obtain mixed suspension. And pouring the mixed suspension into a PTFE (polytetrafluoroethylene) mold for bidirectional freezing, and after the mixed suspension is completely frozen, carrying out freeze drying for 72 hours to obtain the PAAS/GO mixed aerogel. Placing it under the protection of argon gas 300 o C imidization treatment for 4 h, and then 2800 under the protection of argon o And C, performing graphitization treatment for 2 h to obtain the anisotropic high-quality graphene aerogel with a layered structure. Uniformly mixing an epoxy monomer, a diluent, a curing agent and an accelerator according to a ratio, immersing the graphene aerogel, keeping the graphene aerogel under a vacuum condition for 12 hours, taking out the graphene aerogel, and then 80 percent mixing o C reacting for 4 h, 120 o And C, reacting for 2 hours to obtain the composite material, and testing the heat conduction performance of the composite material.
Table 1: thermal conductivity and initial fracture toughness of graphene/epoxy composite materials and epoxy resins obtained in examples 1 to 6
Therefore, the graphene/epoxy resin composite material obtained by the preparation method has high thermal conductivity, the fracture toughness is greatly improved compared with epoxy resin, and the problem that the mechanical property of the composite material is reduced when the filling content is high at present is solved.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto without departing from the scope of the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.
Claims (7)
1. A preparation method of a graphene/epoxy resin composite material based on lamellar anisotropy is characterized by comprising the following steps:
(1) preparing graphene oxide GO and water-soluble polyamic acid salt PAAS;
(2) preparation of anisotropic high-quality graphene aerogel having a layered structure: graphene oxide GO is mixed with water-soluble polyamic acid salt PAAS to obtain GO/PAAS suspension, and the anisotropic high-quality graphene aerogel with a laminated structure is prepared through the steps of bidirectional freezing, freeze drying, imidization treatment and high-temperature graphitization treatment;
(3) preparing a graphene/epoxy resin composite material: compounding the aerogel obtained in the step (2) with an epoxy resin precursor by adopting a vacuum auxiliary impregnation method, compressing the aerogel and the epoxy resin precursor, and heating and curing the compressed aerogel to obtain a graphene/epoxy resin composite material;
in the step (2), the total concentration of the GO and PAAS mixed suspension is 20-60 mg/ml; the mass ratio of GO to PAAS is 3: 7. 4:6 or 5: 5; the imidization treatment temperature is 200-400 DEG C o C；Graphitization temperature is 2800 o C, graphitizing for 60-180 min; all reactions were carried out under argon protection;
in the step (3), the mass ratio of the epoxy resin monomer, the diluent, the curing agent and the accelerator in the epoxy resin precursor is 8:2:9.48: 0.0576; the diluent is ethylene glycol diglycidyl ether, the curing agent is methyl hexahydrophthalic anhydride, and the accelerator is 2,4, 6-tri (dimethylaminomethyl) phenol; the direction of compression of the aerogel is perpendicular to the orientation direction of the lamellar structure; the compression degree is 30-70%; the curing temperature is 80-120 DEG C o And C, the reaction time is 2-4 h.
2. The preparation method according to claim 1, wherein in the step (1), graphite oxide is prepared by a modified Hummers method, and graphene oxide is prepared by subjecting the graphite oxide to ultrasonic treatment; the water-soluble polyamic acid salt is prepared by synthesizing polyamic acid by adopting a condensation polymerization method and then dissolving the polyamic acid in aqueous solution of triethylamine.
3. The method according to claim 2, wherein in the step (1), the Hummers method is: adding potassium permanganate into a mixture of concentrated sulfuric acid, flake graphite and sodium nitrate, performing oxidation reaction, then performing acid washing and water washing, and centrifuging to neutrality to obtain graphite oxide; the ultrasonic treatment time is 1-30 min.
4. The method of claim 3, wherein the condensation polymerization is carried out by: under the protection of nitrogen, adding pyromellitic anhydride into N-N dimethylacetamide solution of 4, 4' -diaminodiphenyl ether, and after the reaction is finished under the ice bath condition, washing, filtering and vacuum-drying the product to obtain polyamic acid; the mass ratio of triethylamine to polyamic acid was (0.4-0.6) to 1.
5. The preparation method according to claim 1, wherein in the step (2), the total concentration of the mixed suspension of GO and PAAS is 40 mg/ml; mass ratio of GO to PAASIs 4: 6; the imidization temperature was 300 deg.C o C; graphitization at 2800 deg.C o And C, the graphitization treatment time is 120 min.
6. The method according to claim 1, wherein in the step (3), the degree of compression is 70%.
7. The graphene/epoxy resin composite material prepared by the preparation method according to any one of claims 1 to 6, wherein the composite material has a shell-like 'brick mud' structure.
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| CN112708152B (en) * | 2020-12-25 | 2022-02-11 | 厦门大学 | Preparation method of high-thermal-conductivity graphite aerogel-based composite thermal interface material |
| CN113941380B (en) * | 2021-10-15 | 2022-10-04 | 深圳市优联半导体有限公司 | Preparation method and application of vertical lamellar orientation structure material |
| CN114891485B (en) * | 2022-06-28 | 2023-03-21 | 湖南大学 | Graphene framework heat-conducting composite material based on three-dimensional vertical arrangement and preparation method thereof |
| CN115340356B (en) * | 2022-07-18 | 2023-04-28 | 华南理工大学 | Metal oxide fiber-graphene composite aerogel and preparation method and application thereof |
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