CN106189088A - A kind of preparation method of CNT graphene oxide hybrid buildup composite - Google Patents

A kind of preparation method of CNT graphene oxide hybrid buildup composite Download PDF

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CN106189088A
CN106189088A CN201610566145.7A CN201610566145A CN106189088A CN 106189088 A CN106189088 A CN 106189088A CN 201610566145 A CN201610566145 A CN 201610566145A CN 106189088 A CN106189088 A CN 106189088A
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graphene oxide
cnt
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composite
hybrid buildup
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CN106189088B (en
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王柏臣
李俊杰
刘永娜
高禹
李伟
马克明
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Huai'an Aviation Industry Research Institute Co., Ltd
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Shenyang Aerospace University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • CCHEMISTRY; METALLURGY
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    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08Materials not undergoing a change of physical state when used
    • C09K5/14Solid materials, e.g. powdery or granular
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/001Conductive additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

Abstract

The invention belongs to polymer matrix composite and manufacture field, be specifically related to the preparation method of a kind of CNT graphene oxide hybrid buildup composite.The present invention is by being assembled into high self-maintaining nano-sized carbon hybrid structure reinforcement by graphene oxide and CNT, infiltrate through resin matrix, after polymerization, obtain CNT graphene oxide hybrid buildup composite, using 2 ethyl 4 Methylimidazole .s as " bridge " between CNT and graphene oxide, preparation low-density and the porous carbon nanotube graphene oxide reinforcement of high-specific surface area, this reinforcement remains the features of graphene oxide and CNT simultaneously, as high conductivity, heat conductivity and the continuous reinforcement of three-dimensional macro are combined with various kinds of resin matrix, preparation cost is low, multi-functional CNT graphene oxide hybrid buildup composite.

Description

A kind of preparation method of CNT-graphene oxide hybrid buildup composite
Technical field
The invention belongs to polymer matrix composite and manufacture field, be specifically related to a kind of CNT-graphene oxide and mix The preparation method of miscellaneous enhancing composite.
Background technology
In recent years, polymer matrix composite is had higher requirement by developing rapidly of science and technology, and collection carries, leads The structure function advanced composite material (ACM)s such as electricity, heat conduction are increasingly subject to people's favor, the novel enhanced of some micro/nano-scales Body is introduced among various thermoplasticity and thermosetting resin matrix, by constructing multi-level macroscopic view continuous structure, greatly carries Rise the performance of polymer matrix composite, widen its range of application further.With CNT and Graphene as representative Nano-carbon material is because having huge specific surface area, excellent mechanical property and heat conductivility at novel energy, biology, electronics Information and field of functional materials receive much concern.Material property fundamentally depends on its internal microstructure, and it is formed and consolidates Change among the forming process of composite.At present, the development of nano carbon composite material is maked rapid progress, but still faces two sides The problem in face: one is formation and the control of nano composite material interior three-dimensional Microscopic order carbon structure;Two is as function carrier This body structure of nano-carbon material and the regulation and control of character.
Nano carbon composite material why have conduction, heat conductivility it is critical only that its inside resin matrix by taking Connecing, be wound macroscopic view contiguous network, this forming process is affected by multiple thermodynamics and kinetics factor.Produce polymerization The traditional method of thing based composites is melt blending or solution blending, in forming process, by ultrasound wave or shear action Realize nano-carbon material dispersed in resin matrix, but this dynamic structure being in thermodynamics non-equilibrium and high length thereof Footpath ratio inevitably leads to the gathering of micro/nano-scale material with carbon element and piles up, and greatly affects CNT and graphene oxide Giving full play to of energy.How realizing nano-carbon material and being internally formed orderly and stable structure at resin matrix is composite neck The general character problem that territory faces.
CNT or Graphene are assembled into three-dimensional nano-sized carbon reinforcement continuously, after compound with resin matrix, three Tieing up continuous nano-sized carbon reinforcement as material function conversion and the material base exported is a kind of promising process route. But, the problem that presently, there are following three aspects: the function aspects anisotropy that (1) is brought by a peacekeeping two-dimensional structure;(2) by Interacted the CNT or the self-maintaining difference of Graphene reinforcement assembled by π-π, has a strong impact on composite structure and property The uniformity of energy;(3) chemical vapor deposition (CVD) method produces CNT and Graphene have the strongest hydrophobicity, are difficult to Fully infiltrated by resin matrix and form strong interfaces and combine.
Summary of the invention
The problem existed for prior art, the present invention provides a kind of CNT-graphene oxide hybrid buildup to be combined The preparation method of material, it is therefore an objective to by graphene oxide and CNT are assembled into high self-maintaining nano-sized carbon hybrid structure Reinforcement, after resin matrix infiltration, polymerization, it is thus achieved that CNT-graphene oxide hybrid buildup composite, with 2-second Base-4-methylimidazole, as " bridge " between CNT and graphene oxide, prepares low-density as shown in Figure 1 and Gao Bi Porous carbon nanotube-graphene oxide the reinforcement of surface area, this reinforcement remains graphene oxide and carbon nanometer simultaneously The features of pipe, is combined with various kinds of resin matrix as the continuous reinforcement of high conductivity, heat conductivity and three-dimensional macro, is prepared as This CNT low, multi-functional-graphene oxide hybrid buildup composite (as shown in Figure 2).
The technical scheme realizing the object of the invention follows the steps below:
(1) by graphene oxide ultrasonic disperse 40 ~ 60 minutes in water, graphene oxide dispersion is obtained;
(2) graphene oxide dispersion that step (1) obtains is warming up to 40oC, adds 2-ethyl-4-methylimidazole, more ultrasonic Disperseing 40 ~ 60 minutes, add CNT, ultrasonic disperse adds ammonia, is warming up to 85 ~ 90 after 2 ~ 3 hoursoC, hydro-thermal reaction 7 ~ 10 hours;
(3), after step (2) gained product being carried out liquid-nitrogen freeze drying process 12 ~ 14 hours, dry 2 ~ 3 hours, obtain Three dimensional carbon nanotubes-graphene oxide hybrid buildup body;
(4) utilizing resin matrix to infiltrate three dimensional carbon nanotubes-graphene oxide reinforcement, moulding process obtains carbon nanometer after processing Pipe-graphene oxide hybrid buildup composite.
Wherein, a diameter of 20-100 μm of step (1) described graphene oxide, the concentration of graphene oxide dispersion is 0.1mg/ml-2mg/ml。
2-ethyl-4-methylimidazole described in step (2) is 1:1 ~ 2 with the weight ratio of graphene oxide.
CNT described in step (2) is that CNT, surface carboxyl groups be carbon nano-tube modified, surface amino groups modified carbon is received Mitron or surface hydroxyl are carbon nano-tube modified, and it is single wall, double-walled or multi-walled carbon nano-tubes.
Ammonia volume described in step (2) is 1 ~ 2ml.
Graphene oxide described in step (2) is 2 ~ 1:1 with the weight ratio of CNT.
Resin matrix described in step (4) is epoxy resin, bimaleimide resin, unsaturated polyester (UP), vinyl tree Any one in fat or cyanate ester resin.
Moulding process described in step (4) is vacuum assisted resin transfer molding (VARTM), Resin Film Infusion (RFI) work Any one in skill or vacuum immersion/mould pressing process.
Compared with prior art, the present invention specific and providing the benefit that:
(1) heterogeneous, multicomponent, multi-level thought are applied to, among novel nanocomposite materials design, utilize oxygen by the present invention Functionalized graphene amphipathic, makes CNT dispersed and collectively as composite inner conduction, heat conduction in water lead to Road.
(2) CNT-graphene oxide reinforcement had both had the polar active group of graphene oxide, has again carbon and receives The high length-diameter ratio of mitron and conduction, the capacity of heat transmission, be conducive to preparation conduction compound with various kinds of resin matrix, heat-conductive composite material.
(3) " bridge " effect of π-π interaction and 2-ethyl-4-methylimidazole, high length-diameter ratio and transverse and longitudinal ratio are utilized Flexible graphene oxide and CNT are assembled into has the most self-maintaining three-dimensional reinforcement, follow-up tree continuously Fat infiltration and forming process.
(4) CNT-electric conductivity of graphene oxide hybrid buildup composite, heat conductivity can aoxidize stone by control Ink alkene size is adjusted with CNT ratio and consumption, and room temperature resistivity reduces by 10 orders of magnitude.
(5) equipment needed thereby of the present invention is simple, with low cost, and technological operation is convenient, can be used for various kinds of resin based composites System.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the CNT-graphene oxide reinforcement of preparation in embodiment 1;
Fig. 2 is the optical photograph of the CNT-graphene oxide hybrid buildup composite of preparation in embodiment 1.
Detailed description of the invention
Following example are to further illustrate the present invention, the epoxy resin of employing, BMI in embodiment Resin, unsaturated polyester (UP), vinylite and cyanate ester resin are commercial products.
The single-walled nanotube specific surface area used in the embodiment of the present invention > 140m2/ g, the specific surface area of double-walled nanotubes > 350m2/ g, the specific surface area of multi-walled carbon nano-tubes > 500m2/ g, is commercial products, a diameter of the 20 of the graphene oxide of employing -100μm。
The ultrasonic field operating frequency used in the embodiment of the present invention is 45kHz, and power is 100W.
Embodiment 1
The preparation method of the CNT of the present embodiment-graphene oxide hybrid buildup composite follows the steps below:
(1) by 0.5g graphene oxide ultrasonic disperse 40 minutes in 2000ml water, the graphene oxide obtaining 0.25mg/ml divides Dissipate liquid;
(2) graphene oxide dispersion that step (1) obtains is warming up to 40oC, adds 0.5g 2-ethyl-4-methylimidazole, Ultrasonic disperse 1 hour again, adds 0.5g multi-walled carbon nano-tubes, and ultrasonic disperse adds 1ml ammonia, is warming up to 90 after 2 hoursoC, water Thermal response 7 hours;
(3), after step (2) gained product being carried out liquid-nitrogen freeze drying process 14 hours, dry 2 hours in 105 DEG C, To three-dimensional multi-walled carbon nano-tubes-graphene oxide hybrid buildup body, its scanning electron microscopic picture is as it is shown in figure 1, can from Fig. 1 Out obtain the CNT-graphene oxide reinforcement of high porosity, specific area, it is possible to be combined with resin matrix Prepare polymer matrix composite;
(4) using mould pressing process molding, multi-walled carbon nano-tubes-graphene oxide hybrid buildup body is put into concentration is 30wt%'s Epoxy resin/acetone glue infiltrates 4 hours, 65 oMove in mould, 80 after drying 2 hours under C oC keeps temperature 20 The pressure 1h of minute after-applied 5MPa, according still further to 80oC/1h, 110oC/2h, 170oC/2h, 200oThe temperature programming solidification of C/1h, Preparing three-dimensional multi-walled carbon nano-tubes-graphene oxide hybrid buildup composite, electrical conductivity is 1 × 10-4Scm-1, thermal conductivity is 0.5Wm-1K-1, its optical photograph is as shown in Figure 2.
Embodiment 2
The preparation method of the CNT of the present embodiment-graphene oxide hybrid buildup composite follows the steps below:
(1) by 1g graphene oxide ultrasonic disperse 60 minutes in 2000ml water, the graphene oxide dispersion of 0.5mg/ml is obtained Liquid;
(2) graphene oxide dispersion that step (1) obtains is warming up to 45oC, adds 1g 2-ethyl-4-methylimidazole, then Ultrasonic disperse 1 hour, adds 1g carboxyl modified multi-walled carbon nano-tubes, and ultrasonic disperse adds 2ml ammonia, is warming up to after 2 hours 90oC, hydro-thermal reaction 10 hours;
(3), after step (2) gained product being carried out liquid-nitrogen freeze drying process 14 hours, dry 2 hours in 105 DEG C, To three-dimensional carboxyl modified multi-walled carbon nano-tubes-graphene oxide hybrid buildup body;
(4) vacuum assisted resin transfer molding technological forming is used, by the carboxyl modified multi-walled carbon nano-tubes-oxidation stone after cutting Ink alkene hybrid buildup body is put in mould, with being preheated to 50oThe epoxy resin of C infiltrates carboxyl modified many walls carbon under vacuum After nanotube-graphene oxide hybrid buildup body, according to 80oC/1h, 110oC/2h, 170oC/2h, 200oThe temperature programming of C/1h Solidification, prepares carboxyl modified multi-walled carbon nano-tubes-graphene oxide hybrid buildup composite, and its electrical conductivity is 2 × 10-4Scm-1, thermal conductivity is 0.3Wm-1K-1
Embodiment 3
The preparation method of the CNT of the present embodiment-graphene oxide hybrid buildup composite follows the steps below:
(1) by 2g graphene oxide ultrasonic disperse 50 minutes in 2000ml water, the graphene oxide dispersion of 1mg/ml is obtained;
(2) graphene oxide dispersion that step (1) obtains is warming up to 42oC, adds 1g 2-ethyl-4-methylimidazole, then Ultrasonic disperse 1 hour, adds 1g hydroxyl modified multi-walled carbon nano-tubes, and ultrasonic disperse adds 1ml ammonia, is warming up to after 2 hours 85oC, hydro-thermal reaction 8 hours;
(3), after step (2) gained product being carried out liquid-nitrogen freeze drying process 13 hours, dry 2 hours in 105 DEG C, To three-dimensional hydroxyl modified multi-walled carbon nano-tubes-graphene oxide hybrid buildup body;
(4) use Resin film infusion molding, epoxy resin is placed in mould, place the hydroxyl after cutting the most in the above Base modifying multiwall carbon nano-tube-graphene oxide reinforcement, then closes with vacuum bag, is heated to 50oEvacuation after C, epoxy After resin infiltration hydroxylating CNT-graphene oxide hybrid buildup body, according to 80oC/1h, 110oC/2h, 170oC/2h, 200oThe temperature programming solidification of C/1h, prepares hydroxylating multi-walled carbon nano-tubes-graphene oxide hybrid buildup composite, its electricity Conductance is 1.3 × 10-4Scm-1, thermal conductivity is 0.58Wm-1K-1
Embodiment 4
The preparation method of the CNT of the present embodiment-graphene oxide hybrid buildup composite follows the steps below:
(1) by 2g graphene oxide ultrasonic disperse 40 minutes in 2000ml water, the graphene oxide dispersion of 1mg/ml is obtained;
(2) graphene oxide dispersion that step (1) obtains is warming up to 40oC, adds 2g 2-ethyl-4-methylimidazole, then Ultrasonic disperse 1 hour, adds the amido modified multi-walled carbon nano-tubes of 2g, and ultrasonic disperse adds 1ml ammonia, is warming up to after 2 hours 85oC, hydro-thermal reaction 8 hours;
(3), after step (2) gained product being carried out liquid-nitrogen freeze drying process 14 hours, dry 2 hours in 105 DEG C, To three-dimensional amino-group modifying multiwall carbon nano-tube-graphene oxide hybrid buildup body;
(4) vacuum assisted resin transfer molding technological forming is used, by the amido modified multi-walled carbon nano-tubes-oxidation stone after cutting Ink alkene hybrid buildup body is put in mould, with being preheated to 40oThe cyanate ester resin of C infiltrates amido modified many walls under vacuum After CNT-graphene oxide hybrid buildup body, according to 110oC/1h, 170oC/2h, 200oThe temperature programming solidification of C/1h, Preparing amido modified multi-walled carbon nano-tubes-graphene oxide hybrid buildup composite, electrical conductivity is 3 × 10-4Scm-1, thermal conductance Rate is 0.25Wm-1K-1

Claims (8)

1. the preparation method of CNT-graphene oxide hybrid buildup composite, it is characterised in that according to following step Suddenly carry out:
(1) by graphene oxide ultrasonic disperse 40 ~ 60 minutes in water, graphene oxide dispersion is obtained;
(2) graphene oxide dispersion that step (1) obtains is warming up to 40oC, adds 2-ethyl-4-methylimidazole, more ultrasonic Disperseing 40 ~ 60 minutes, add CNT, ultrasonic disperse adds ammonia, is warming up to 85 ~ 90 after 2 ~ 3 hoursoC, hydro-thermal reaction 7 ~ 10 hours;
(3), after step (2) gained product being carried out liquid-nitrogen freeze drying process 12 ~ 14 hours, dry 2 ~ 3 hours, obtain Three dimensional carbon nanotubes-graphene oxide hybrid buildup body;
(4) utilizing resin matrix to infiltrate three dimensional carbon nanotubes-graphene oxide reinforcement, moulding process obtains carbon nanometer after processing Pipe-graphene oxide hybrid buildup composite.
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid buildup composite, its Being characterised by a diameter of 20-100 μm of step (1) described graphene oxide, the concentration of graphene oxide dispersion is 0.1mg/ ml-2mg/ml。
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid buildup composite, its It is characterised by that 2-ethyl-4-methylimidazole described in step (2) is 1:1 ~ 2 with the weight ratio of graphene oxide.
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid buildup composite, its It is characterised by that the CNT described in step (2) is that CNT, surface carboxyl groups be carbon nano-tube modified, surface amino groups modified carbon is received Mitron or surface hydroxyl are carbon nano-tube modified, and it is single wall, double-walled or multi-walled carbon nano-tubes.
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid buildup composite, its It is characterised by that the ammonia volume described in step (2) is 1 ~ 2ml.
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid buildup composite, its It is characterised by that graphene oxide described in step (2) is 2 ~ 1:1 with the weight ratio of CNT.
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid buildup composite, its It is characterised by that the resin matrix described in step (4) is epoxy resin, bimaleimide resin, unsaturated polyester (UP), vinyl tree Any one in fat or cyanate ester resin.
The preparation method of a kind of CNT the most according to claim 1-graphene oxide hybrid buildup composite, its Be characterised by the moulding process described in step (4) be vacuum assisted resin transfer molding, Resin film infusion or vacuum immersion/ Any one in mould pressing process.
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CN107099833A (en) * 2017-03-29 2017-08-29 广东工业大学 A kind of composite plating solution and preparation method thereof
CN107141794A (en) * 2017-06-20 2017-09-08 苏州大学 A kind of resin base brush and preparation method thereof
CN107286491A (en) * 2017-06-16 2017-10-24 青岛大学 A kind of high conductivity carbon nano tube/graphene aeroge/poly styrene composite material and preparation method thereof
CN108774421A (en) * 2018-07-12 2018-11-09 山东佳星环保科技有限公司 A kind of graphene composite wave-suction material and preparation method thereof and coating agent using the material preparation
CN109021930A (en) * 2018-08-13 2018-12-18 陕西理工大学 A kind of carbon aerogels composite shape-stabilized phase change energy storage material and preparation method thereof
CN109735064A (en) * 2018-12-27 2019-05-10 重庆墨希科技有限公司 A kind of conductive agglomerate and preparation method thereof
CN110724214A (en) * 2019-09-17 2020-01-24 沈阳航空航天大学 Preparation method of heat-conducting porous hybrid composite material
CN111113946A (en) * 2019-12-17 2020-05-08 江苏理工学院 Hybrid composite laminated board and preparation process thereof
CN111155325A (en) * 2020-01-22 2020-05-15 黎明化工研究设计院有限责任公司 Three-dimensional composite nano carbon material, environment-friendly polyurethane synthetic leather with high folding fastness prepared from three-dimensional composite nano carbon material and preparation method of environment-friendly polyurethane synthetic leather
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CN113088037A (en) * 2021-04-13 2021-07-09 珠海昌意新材料科技有限公司 Heat dissipation material with high heat conductivity coefficient and high radiation coefficient and preparation method thereof
CN114836645A (en) * 2022-04-06 2022-08-02 西北工业大学 Preparation method of carbon nanotube-graphene hybrid porous preform with designable configuration

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CN107099833A (en) * 2017-03-29 2017-08-29 广东工业大学 A kind of composite plating solution and preparation method thereof
CN107286491B (en) * 2017-06-16 2020-02-07 青岛大学 High-conductivity carbon nanotube/graphene aerogel/polystyrene composite material and preparation method thereof
CN107286491A (en) * 2017-06-16 2017-10-24 青岛大学 A kind of high conductivity carbon nano tube/graphene aeroge/poly styrene composite material and preparation method thereof
CN107141794A (en) * 2017-06-20 2017-09-08 苏州大学 A kind of resin base brush and preparation method thereof
CN108774421A (en) * 2018-07-12 2018-11-09 山东佳星环保科技有限公司 A kind of graphene composite wave-suction material and preparation method thereof and coating agent using the material preparation
CN109021930A (en) * 2018-08-13 2018-12-18 陕西理工大学 A kind of carbon aerogels composite shape-stabilized phase change energy storage material and preparation method thereof
CN109735064A (en) * 2018-12-27 2019-05-10 重庆墨希科技有限公司 A kind of conductive agglomerate and preparation method thereof
CN110724214A (en) * 2019-09-17 2020-01-24 沈阳航空航天大学 Preparation method of heat-conducting porous hybrid composite material
CN110724214B (en) * 2019-09-17 2022-06-10 沈阳航空航天大学 Preparation method of heat-conducting porous hybrid composite material
CN111113946A (en) * 2019-12-17 2020-05-08 江苏理工学院 Hybrid composite laminated board and preparation process thereof
CN111151765A (en) * 2020-01-20 2020-05-15 西安稀有金属材料研究院有限公司 Preparation method of three-dimensional structure nano carbon material reinforced copper-based composite material
CN111155325A (en) * 2020-01-22 2020-05-15 黎明化工研究设计院有限责任公司 Three-dimensional composite nano carbon material, environment-friendly polyurethane synthetic leather with high folding fastness prepared from three-dimensional composite nano carbon material and preparation method of environment-friendly polyurethane synthetic leather
CN111155325B (en) * 2020-01-22 2022-08-30 黎明化工研究设计院有限责任公司 Three-dimensional composite nano carbon material, environment-friendly polyurethane synthetic leather with high folding fastness prepared from three-dimensional composite nano carbon material and preparation method of environment-friendly polyurethane synthetic leather
CN113088037A (en) * 2021-04-13 2021-07-09 珠海昌意新材料科技有限公司 Heat dissipation material with high heat conductivity coefficient and high radiation coefficient and preparation method thereof
CN114836645A (en) * 2022-04-06 2022-08-02 西北工业大学 Preparation method of carbon nanotube-graphene hybrid porous preform with designable configuration

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