CN111269570A - Preparation method of carbonized towel gourd/graphene-carbon nanotube composite material - Google Patents

Preparation method of carbonized towel gourd/graphene-carbon nanotube composite material Download PDF

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CN111269570A
CN111269570A CN202010214953.3A CN202010214953A CN111269570A CN 111269570 A CN111269570 A CN 111269570A CN 202010214953 A CN202010214953 A CN 202010214953A CN 111269570 A CN111269570 A CN 111269570A
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graphene
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carbon nanotube
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loofah
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CN111269570B (en
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任鹏刚
郭铮铮
宗泽
任芳
靳彦岭
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Xi'an Haoyou Aerospace Composite Material Co ltd
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Xian University of Technology
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Abstract

The invention discloses a preparation method of a carbonized towel gourd/graphene-carbon nanotube composite material, which comprises the following steps: dispersing graphene and carbon nanotubes in a polyvinyl alcohol solution, pouring the polyvinyl alcohol solution on rectangular loofah sponge, drying in vacuum, compacting, then putting the rectangular loofah sponge into a tube furnace for carbonization to obtain a CL/GNSs-CNT composite material, mixing and stirring cyanate and epoxy resin, then casting the mixture on the CL/GNSs-CNT composite material, and curing to obtain the carbonized loofah/graphene-carbon nanotube/cyanate resin composite material. The CL/GNSs-CNT/CE composite material prepared by the method has excellent electromagnetic shielding performance and certain mechanical property, and can meet the application requirements in the fields of aerospace, electronic packaging and the like.

Description

一种碳化丝瓜/石墨烯-碳纳米管复合材料的制备方法A kind of preparation method of carbonized loofah/graphene-carbon nanotube composite material

技术领域technical field

本发明属于复合材料制备技术领域,具体涉及一种碳化丝瓜/石墨烯-碳纳米管复合材料的制备方法。The invention belongs to the technical field of composite material preparation, and in particular relates to a preparation method of a carbonized loofah/graphene-carbon nanotube composite material.

背景技术Background technique

随着电子器件和电磁波技术在民用和军用领域的发展,电磁波污染已日益成为威胁人类健康和附近器件固有性能的严重威胁。因此,设计和制备具有较强屏蔽性能和环境适应性的高效电磁干扰(EMI)屏蔽材料对解决这一问题具有十分重要的意义。With the development of electronic devices and electromagnetic wave technology in civil and military fields, electromagnetic wave pollution has increasingly become a serious threat to human health and the inherent performance of nearby devices. Therefore, the design and preparation of high-efficiency electromagnetic interference (EMI) shielding materials with strong shielding performance and environmental adaptability are of great significance to solve this problem.

多孔结构的形成是显著缓解电磁波从空气中传播到电磁屏蔽材料中的一个重大技术进步,使二次电磁辐射污染显著降低。近年来,生物质炭以其优异的性能和环保的特性,在电催化剂、CO2吸附剂、超级电容器、电磁波吸收剂等领域有着广阔的应用前景。丝瓜是世界上最常见的生物原料之一,广泛种植于温带和热带地区,具有一定的食用和药用价值。它由纤维素、半纤维素和木质素组成。其关键是天然丝瓜经炭化后,呈现出微观的细胞结构,并保持原有的形态特征,这有利于构建完整的三维互连导电网络,并因其独特的蜂窝状多孔结构而被视为电磁屏蔽的先进候选材料。为了进一步提高炭化生物质基原材料的导电性,从而提高其EMI-SE值,可以将AgNWs、碳纳米管(CNT)和石墨烯纳米片(GNSs)等二次导电填料引入到所制备的复合材料中。其中,CNT和GNSs具有超高导电性、重量轻、耐腐蚀、热稳定性高等特点,已被证明是一种优良的电磁屏蔽材料。研究表明,复合材料的三维高连通导电网络对其导电性和电磁屏蔽效果起着至关重要的作用。考虑到快速发展的航空航天和国防应用的迫切需求,氰酸酯(CE)以其极低的吸湿性、良好的力学性能、优异的抗辐射性能和优异的尺寸稳定性被用作聚合物基体。The formation of porous structures is a major technological advance in significantly mitigating the propagation of electromagnetic waves from the air into electromagnetic shielding materials, resulting in a significant reduction in secondary electromagnetic radiation pollution. In recent years, biomass carbon has broad application prospects in the fields of electrocatalysts, CO2 adsorbents, supercapacitors, electromagnetic wave absorbers, etc. due to its excellent performance and environmental protection characteristics. Luffa is one of the most common biological raw materials in the world. It is widely grown in temperate and tropical regions and has certain edible and medicinal value. It consists of cellulose, hemicellulose and lignin. The key is that after carbonization, natural loofah exhibits a microscopic cellular structure and maintains the original morphological characteristics, which is conducive to the construction of a complete three-dimensional interconnected conductive network, and is regarded as electromagnetic due to its unique honeycomb-like porous structure. Advanced candidate materials for shielding. In order to further enhance the electrical conductivity of carbonized biomass-based raw materials, thereby enhancing their EMI-SE values, secondary conductive fillers such as AgNWs, carbon nanotubes (CNTs), and graphene nanosheets (GNSs) can be introduced into the as-prepared composites middle. Among them, CNTs and GNSs have the characteristics of ultra-high electrical conductivity, light weight, corrosion resistance, and high thermal stability, and have been proven to be excellent electromagnetic shielding materials. The study shows that the three-dimensional highly connected conductive network of the composite material plays a crucial role in its electrical conductivity and electromagnetic shielding effect. Considering the urgent needs of rapidly developing aerospace and defense applications, cyanate esters (CE) are used as polymer matrices due to their extremely low hygroscopicity, good mechanical properties, excellent radiation resistance and excellent dimensional stability .

发明内容SUMMARY OF THE INVENTION

本发明的目的在于提供一种碳化丝瓜/石墨烯-碳纳米管(CL/GNSs-CNT/CE)复合材料的制备方法,解决了现有技术中复合材料电磁屏蔽性能低的问题。The purpose of the present invention is to provide a preparation method of a carbonized loofah/graphene-carbon nanotube (CL/GNSs-CNT/CE) composite material, which solves the problem of low electromagnetic shielding performance of the composite material in the prior art.

本发明所采用的技术方案是,一种碳化丝瓜/石墨烯-碳纳米管复合材料的制备方法,具体步骤如下:The technical solution adopted in the present invention is, a preparation method of a carbonized loofah/graphene-carbon nanotube composite material, the specific steps are as follows:

步骤1,将聚乙烯醇颗粒溶于去离子水中,于90℃水浴锅中反应1~2h,得到质量浓度为80mg/mL的聚乙烯醇溶液;Step 1, dissolving the polyvinyl alcohol particles in deionized water, and reacting in a 90° C. water bath for 1-2 hours to obtain a polyvinyl alcohol solution with a mass concentration of 80 mg/mL;

步骤2,将石墨烯和碳纳米管分散在聚乙烯醇溶液中,超声搅拌,得到石墨烯-碳纳米管/聚乙烯醇溶液;Step 2, dispersing graphene and carbon nanotubes in a polyvinyl alcohol solution, and ultrasonically stirring to obtain a graphene-carbon nanotube/polyvinyl alcohol solution;

步骤3,制备碳化丝瓜/石墨烯-碳纳米管复合材料;Step 3, preparing carbonized loofah/graphene-carbon nanotube composite material;

步骤4,制备碳化丝瓜/石墨烯-碳纳米管/氰酸酯树脂复合材料。Step 4, preparing the carbonized loofah/graphene-carbon nanotube/cyanate resin composite material.

本发明的特点还在于,The present invention is also characterized in that,

步骤2中,石墨烯、碳纳米管和聚乙烯醇溶液的质量比为0.025-0.062:0.008:10;搅拌时间为30min~60min。In step 2, the mass ratio of graphene, carbon nanotubes and polyvinyl alcohol solution is 0.025-0.062:0.008:10; the stirring time is 30min-60min.

步骤3中,制备碳化丝瓜/石墨烯-碳纳米管复合材料,具体步骤如下:In step 3, the carbonized loofah/graphene-carbon nanotube composite material is prepared, and the specific steps are as follows:

步骤3.1,将丝瓜络清洗干净,切成尺寸为40×30mm的矩形丝瓜络,放置在60℃的真空烘箱中干燥4h,将石墨烯-碳纳米管/聚乙烯醇溶液浇在矩形丝瓜络上,放置在60℃真空烘箱中干燥4h后压实;Step 3.1, clean the loofah, cut it into a rectangular loofah with a size of 40×30mm, place it in a vacuum oven at 60°C for 4 hours, and pour the graphene-carbon nanotube/polyvinyl alcohol solution on the rectangular loofah , placed in a 60°C vacuum oven to dry for 4 hours and then compacted;

矩形丝瓜络和石墨烯-碳纳米管/聚乙烯醇溶液的质量比为3:10;The mass ratio of rectangular loofah and graphene-carbon nanotube/polyvinyl alcohol solution is 3:10;

步骤3.2,将压实的矩形丝瓜络放入管式炉中进行碳化,得到碳化丝瓜/石墨烯-碳纳米管复合材料。Step 3.2, putting the compacted rectangular loofah into a tube furnace for carbonization to obtain a carbonized loofah/graphene-carbon nanotube composite material.

步骤3.2中,碳化条件具体为:以50~100mL/s的速率通入氮气,以5℃/min的速率升温至800~1200℃并保温2h,冷却至室温。In step 3.2, the carbonization conditions are as follows: nitrogen is introduced at a rate of 50-100 mL/s, the temperature is raised to 800-1200° C. at a rate of 5° C./min, kept for 2 hours, and cooled to room temperature.

步骤4中,具体为:将氰酸酯和环氧树脂混合,在80℃的条件下搅拌30min,之后浇铸在碳化丝瓜/石墨烯-碳纳米管复合材料上,先于120℃的条件下固化1h,再于150℃的条件下固化2h,之后再于180℃的条件下固化2h,最后于200℃的条件下固化2h,得到碳化丝瓜/石墨烯-碳纳米管/氰酸酯树脂复合材料。In step 4, specifically: mixing cyanate ester and epoxy resin, stirring at 80°C for 30 minutes, then casting on the carbonized loofah/graphene-carbon nanotube composite material, and curing at 120°C first 1h, then cured at 150°C for 2h, then cured at 180°C for 2h, and finally cured at 200°C for 2h to obtain the carbonized loofah/graphene-carbon nanotube/cyanate resin composite material .

氰酸酯、环氧树脂和碳化丝瓜/石墨烯-碳纳米管复合材料的质量比为4:1:8。The mass ratio of cyanate ester, epoxy resin and carbonized loofah/graphene-carbon nanotube composite was 4:1:8.

本发明的有益效果是,通过高度互联三维导电网络的设计,制备出了低填料、低厚度、高电磁屏蔽性能的复合材料;同时,该制备方法简便可行,具有较低的生产成本,易于批量化生产。The beneficial effect of the present invention is that, through the design of a highly interconnected three-dimensional conductive network, a composite material with low filler, low thickness and high electromagnetic shielding performance is prepared; at the same time, the preparation method is simple and feasible, has low production cost, and is easy to batch. production.

附图说明Description of drawings

图1是本发明方法中不同石墨烯含量下CL/GNSs-CNT/CE复合材料的总电磁屏蔽效能(SET)图;Fig. 1 is the total electromagnetic shielding effectiveness (SET) figure of CL/ GNSs -CNT/CE composite material under different graphene contents in the method of the present invention;

图2是本发明方法中不同石墨烯含量下CL/GNSs-CNT/CE复合材料的SER、SEA图;Fig. 2 is the SER, SE A figure of CL/ GNSs -CNT/CE composite material under different graphene contents in the method of the present invention;

图3是本发明方法中不同碳化温度下CL/GNSs-CNT/CE复合材料的总电磁屏蔽效能(SET)图;3 is a graph of the total electromagnetic shielding effectiveness (SET ) of CL/ GNSs -CNT/CE composites at different carbonization temperatures in the method of the present invention;

图4是本发明方法中不同碳化温度下CL/GNSs-CNT/CE复合材料的SER、SEA图。4 is the SER and SE A diagrams of the CL/GNSs-CNT/CE composite material at different carbonization temperatures in the method of the present invention .

具体实施方式Detailed ways

下面结合附图和具体实施方式对本发明进行详细说明。The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

本发明一种碳化丝瓜/石墨烯-碳纳米管(CL/GNSs-CNT/CE)复合材料的制备方法,具体步骤如下:The present invention is a preparation method of carbonized loofah/graphene-carbon nanotube (CL/GNSs-CNT/CE) composite material, and the specific steps are as follows:

步骤1,将聚乙烯醇颗粒溶于去离子水中,于90℃水浴锅中反应1~2h,得到质量浓度为80mg/mL的聚乙烯醇溶液;Step 1, dissolving the polyvinyl alcohol particles in deionized water, and reacting in a 90° C. water bath for 1-2 hours to obtain a polyvinyl alcohol solution with a mass concentration of 80 mg/mL;

步骤2,将石墨烯和碳纳米管分散在聚乙烯醇溶液中,超声搅拌30min~60min,得到石墨烯-碳纳米管/聚乙烯醇溶液;Step 2, dispersing graphene and carbon nanotubes in a polyvinyl alcohol solution, and ultrasonically stirring for 30-60 minutes to obtain a graphene-carbon nanotube/polyvinyl alcohol solution;

石墨烯、碳纳米管和聚乙烯醇溶液的质量比为0.025-0.062:0.008:10;The mass ratio of graphene, carbon nanotubes and polyvinyl alcohol solution is 0.025-0.062:0.008:10;

石墨烯的生产产家分别为厦门Knano石墨烯公司;碳纳米管的生产产家为比利时Nanocyl S.A.Nanocyl NC7000。The producers of graphene are Xiamen Knano Graphene Company; the producer of carbon nanotubes is Belgian Nanocyl S.A. Nanocyl NC7000.

石墨烯的厚度<30nm;碳纳米管的平均直径是9.5nm;The thickness of graphene is <30nm; the average diameter of carbon nanotubes is 9.5nm;

步骤3,制备碳化丝瓜/石墨烯-碳纳米管(CL/GNSs-CNT)复合材料,具体步骤如下:Step 3, preparing the carbonized loofah/graphene-carbon nanotube (CL/GNSs-CNT) composite material, the specific steps are as follows:

步骤3.1,将丝瓜络清洗干净,切成尺寸为40×30mm的矩形丝瓜络,放置在60℃的真空烘箱中干燥4h,将石墨烯-碳纳米管/聚乙烯醇溶液浇在矩形丝瓜络上,使溶液均匀包裹在矩形丝瓜络纤维上,放置在60℃真空烘箱中干燥4h后压实;Step 3.1, clean the loofah, cut it into a rectangular loofah with a size of 40×30mm, place it in a vacuum oven at 60°C for 4 hours, and pour the graphene-carbon nanotube/polyvinyl alcohol solution on the rectangular loofah , so that the solution is evenly wrapped on the rectangular loofah fibers, placed in a vacuum oven at 60 °C for 4 hours, and then compacted;

矩形丝瓜络和石墨烯-碳纳米管/聚乙烯醇溶液的质量比为3:10;The mass ratio of rectangular loofah and graphene-carbon nanotube/polyvinyl alcohol solution is 3:10;

步骤3.2,将压实的矩形丝瓜络放入管式炉中进行碳化,得到碳化丝瓜/石墨烯-碳纳米管(CL/GNSs-CNT)复合材料;Step 3.2, putting the compacted rectangular loofah into a tube furnace for carbonization to obtain a carbonized loofah/graphene-carbon nanotube (CL/GNSs-CNT) composite material;

碳化条件具体为:以50~100mL/s的速率通入氮气,以5℃/min的速率升温至800~1200℃并保温2h,冷却至室温;The carbonization conditions are as follows: nitrogen is introduced at a rate of 50-100 mL/s, heated to 800-1200°C at a rate of 5°C/min, kept for 2 hours, and cooled to room temperature;

步骤4,制备碳化丝瓜/石墨烯-碳纳米管/氰酸酯树脂(CL/GNSs-CNT/CE)复合材料;Step 4, preparing carbonized loofah/graphene-carbon nanotube/cyanate resin (CL/GNSs-CNT/CE) composite material;

具体为:将氰酸酯(BADCy)和环氧树脂(E-51)混合,在80℃的条件下搅拌30min,之后浇铸在CL/GNSs-CNT复合材料上,先于120℃的条件下固化1h,再于150℃的条件下固化2h,之后再于180℃的条件下固化2h,最后于200℃的条件下固化2h,得到碳化丝瓜/石墨烯-碳纳米管/氰酸酯树脂(CL/GNSs-CNT/CE)复合材料。Specifically: mix cyanate ester (BADCy) and epoxy resin (E-51), stir at 80°C for 30min, cast on CL/GNSs-CNT composite material, and cure at 120°C first 1 h, then cured at 150 °C for 2 h, then cured at 180 °C for 2 h, and finally cured at 200 °C for 2 h to obtain carbonized loofah/graphene-carbon nanotubes/cyanate resin (CL /GNSs-CNT/CE) composites.

氰酸酯、环氧树脂和CL/GNSs-CNT复合材料的质量比为4:1:8。The mass ratio of cyanate ester, epoxy resin and CL/GNSs-CNT composite was 4:1:8.

实施例1Example 1

一种CL/GNSs-CNT/CE复合材料的制备方法,具体步骤如下:A preparation method of CL/GNSs-CNT/CE composite material, the specific steps are as follows:

步骤1,将8g聚乙烯醇颗粒溶于92ml去离子水中,于90℃水浴锅中反应1h,得到质量浓度为80mg/mL的聚乙烯醇溶液;Step 1, dissolve 8g of polyvinyl alcohol particles in 92ml of deionized water, and react in a 90°C water bath for 1 hour to obtain a polyvinyl alcohol solution with a mass concentration of 80mg/mL;

步骤2,将3wt%石墨烯和1wt%碳纳米管分散在10ml上述聚乙烯醇溶液中,超声搅拌30min~60min,得到石墨烯-碳纳米管/聚乙烯醇溶液;Step 2, dispersing 3wt% graphene and 1wt% carbon nanotubes in 10ml of the above polyvinyl alcohol solution, and ultrasonically stirring for 30min-60min to obtain a graphene-carbon nanotube/polyvinyl alcohol solution;

步骤3,制备CL/GNSs-CNT复合材料,具体步骤如下:Step 3, prepare the CL/GNSs-CNT composite material, and the specific steps are as follows:

步骤3.1,将丝瓜络洗净,切取40×30mm大小的矩形,放置在60℃真空烘箱中烘干,将石墨烯-碳纳米管/聚乙烯醇溶液浇在丝瓜络上,使溶液均匀包裹在丝瓜络纤维上,放置在60℃真空烘箱中烘干后压实;Step 3.1, wash the loofah, cut a rectangle of size 40×30mm, place it in a 60°C vacuum oven to dry, pour the graphene-carbon nanotube/polyvinyl alcohol solution on the loofah, and make the solution evenly wrapped in the loofah. On the loofah fiber, place it in a 60°C vacuum oven to dry and compact it;

步骤3.2,将上述被压实的丝瓜放入管式炉专用的矩形船中,在均匀的氮气气氛中,800℃下保温2h,升温速率为5℃/min,得到CL/GNSs-CNT复合材料;Step 3.2, put the above-mentioned compacted loofah into a rectangular boat dedicated to the tube furnace, and keep it at 800 °C for 2 h in a uniform nitrogen atmosphere, with a heating rate of 5 °C/min to obtain a CL/GNSs-CNT composite material ;

步骤4,制备CL/GNSs-CNT/CE复合材料;Step 4, preparing CL/GNSs-CNT/CE composite material;

具体为:将2g氰酸酯(BADCy)和0.5g环氧树脂(E-51)在80℃下混合,搅拌30min,然后浇铸在CL/GNSs-CNT上,先于120℃的条件下固化1h,再于150℃的条件下固化2h,之后再于180℃的条件下固化2h,最后于200℃的条件下固化2h,得到CL/GNSs-CNT/CE复合材料。Specifically: mix 2g cyanate ester (BADCy) and 0.5g epoxy resin (E-51) at 80°C, stir for 30min, then cast on CL/GNSs-CNT, and cure at 120°C for 1h first , and then cured at 150 °C for 2 h, then at 180 °C for 2 h, and finally at 200 °C for 2 h to obtain CL/GNSs-CNT/CE composites.

相比于商用的电磁屏蔽材料(20dB),实施例1制备的CL/GNSs-CNT/CE复合材料的电磁屏蔽效能为23.6dB,相应的提高了18%。Compared with the commercial electromagnetic shielding material (20dB), the electromagnetic shielding efficiency of the CL/GNSs-CNT/CE composite prepared in Example 1 is 23.6dB, a corresponding increase of 18%.

实施例2Example 2

一种CL/GNSs-CNT/CE复合材料的制备方法,具体步骤如下:A preparation method of CL/GNSs-CNT/CE composite material, the specific steps are as follows:

步骤1,将8g聚乙烯醇颗粒溶于92ml去离子水中,于90℃水浴锅中反应1~2h,得到质量浓度为80mg/ml的聚乙烯醇溶液;Step 1, dissolve 8g of polyvinyl alcohol particles in 92ml of deionized water, and react in a 90°C water bath for 1 to 2 hours to obtain a polyvinyl alcohol solution with a mass concentration of 80mg/ml;

步骤2,将5wt%石墨烯和1wt%碳纳米管分散在10ml上述聚乙烯醇溶液中,超声搅拌40min,得到石墨烯-碳纳米管/聚乙烯醇溶液;Step 2, dispersing 5wt% graphene and 1wt% carbon nanotubes in 10ml of the above polyvinyl alcohol solution, and ultrasonically stirring for 40min to obtain a graphene-carbon nanotube/polyvinyl alcohol solution;

步骤3,制备CL/GNSs-CNT复合材料,具体步骤如下:Step 3, prepare the CL/GNSs-CNT composite material, and the specific steps are as follows:

步骤3.1,将丝瓜络洗净,切取40×30mm大小的矩形,放置在60℃真空烘箱中烘干,将石墨烯-碳纳米管/聚乙烯醇溶液浇在丝瓜络上,使溶液均匀包裹在丝瓜络纤维上,放置在60℃真空烘箱中烘干后压实;Step 3.1, wash the loofah, cut a rectangle of size 40×30mm, place it in a 60°C vacuum oven to dry, pour the graphene-carbon nanotube/polyvinyl alcohol solution on the loofah, and make the solution evenly wrapped in the loofah. On the loofah fiber, place it in a 60°C vacuum oven to dry and compact it;

步骤3.2,将上述被压实的丝瓜放入管式炉专用的矩形船中,在均匀的氮气气氛中,800℃下保温2h,升温速率为5℃/min,得到CL/GNSs-CNT复合材料;Step 3.2, put the above-mentioned compacted loofah into a rectangular boat dedicated to the tube furnace, and keep it at 800 °C for 2 h in a uniform nitrogen atmosphere, with a heating rate of 5 °C/min to obtain a CL/GNSs-CNT composite material ;

步骤4,制备CL/GNSs-CNT/CE复合材料:Step 4, preparation of CL/GNSs-CNT/CE composites:

具体为:将2g氰酸酯(BADCy)和0.5g环氧树脂(E-51)在80℃下混合,搅拌30min,然后浇铸在CL/GNSs-CNT上,先于120℃的条件下固化1h,再于150℃的条件下固化2h,之后再于180℃的条件下固化2h,最后于200℃的条件下固化2h,得到CL/GNSs-CNT/CE复合材料。Specifically: mix 2g cyanate ester (BADCy) and 0.5g epoxy resin (E-51) at 80°C, stir for 30min, then cast on CL/GNSs-CNT, and cure at 120°C for 1h first , and then cured at 150 °C for 2 h, then at 180 °C for 2 h, and finally at 200 °C for 2 h to obtain CL/GNSs-CNT/CE composites.

相比于商用的电磁屏蔽材料(20dB),实施例2制备的CL/GNSs-CNT/CE复合材料的电磁屏蔽效能为25.9dB,相应的提高了29.5%。Compared with the commercial electromagnetic shielding material (20dB), the electromagnetic shielding efficiency of the CL/GNSs-CNT/CE composite prepared in Example 2 is 25.9dB, a corresponding increase of 29.5%.

实施例3Example 3

一种CL/GNSs-CNT/CE复合材料的制备方法,具体步骤如下:A preparation method of CL/GNSs-CNT/CE composite material, the specific steps are as follows:

步骤1,将8g聚乙烯醇颗粒溶于92ml去离子水中,于90℃水浴锅中反应1~2h,得到质量浓度为80mg/ml的聚乙烯醇溶液;Step 1, dissolve 8g of polyvinyl alcohol particles in 92ml of deionized water, and react in a 90°C water bath for 1 to 2 hours to obtain a polyvinyl alcohol solution with a mass concentration of 80mg/ml;

步骤2,将7wt%石墨烯和1wt%碳纳米管分散在10ml上述聚乙烯醇溶液中,超声搅拌45min,得到石墨烯-碳纳米管/聚乙烯醇溶液;Step 2, dispersing 7wt% graphene and 1wt% carbon nanotubes in 10ml of the above polyvinyl alcohol solution, and ultrasonically stirring for 45min to obtain a graphene-carbon nanotube/polyvinyl alcohol solution;

步骤3,制备CL/GNSs-CNT复合材料,具体步骤如下:Step 3, prepare the CL/GNSs-CNT composite material, and the specific steps are as follows:

步骤3.1,将丝瓜络洗净,切取40×30mm大小的矩形,放置在60℃真空烘箱中烘干,将石墨烯-碳纳米管/聚乙烯醇溶液浇在丝瓜络上,使溶液均匀包裹在丝瓜络纤维上,放置在60℃真空烘箱中烘干后压实;Step 3.1, wash the loofah, cut a rectangle of size 40×30mm, place it in a 60°C vacuum oven to dry, pour the graphene-carbon nanotube/polyvinyl alcohol solution on the loofah, and make the solution evenly wrapped in the loofah. On the loofah fiber, place it in a 60°C vacuum oven to dry and compact it;

步骤3.2,将上述被压实的丝瓜放入管式炉专用的矩形船中,在均匀的氮气气氛中,800℃下保温2h,升温速率为5℃/min,得到CL/GNSs-CNT复合材料;Step 3.2, put the above-mentioned compacted loofah into a rectangular boat dedicated to the tube furnace, and keep it at 800 °C for 2 h in a uniform nitrogen atmosphere, with a heating rate of 5 °C/min to obtain a CL/GNSs-CNT composite material ;

步骤4,制备CL/GNSs-CNT/CE复合材料:Step 4, preparation of CL/GNSs-CNT/CE composites:

具体为:将2g氰酸酯(BADCy)和0.5g环氧树脂(E-51)在80℃下混合,搅拌30min,然后浇铸在CL/GNSs-CNT上,先于120℃的条件下固化1h,再于150℃的条件下固化2h,之后再于180℃的条件下固化2h,最后于200℃的条件下固化2h,得到CL/GNSs-CNT/CE复合材料。Specifically: mix 2g cyanate ester (BADCy) and 0.5g epoxy resin (E-51) at 80°C, stir for 30min, then cast on CL/GNSs-CNT, and cure at 120°C for 1h first , and then cured at 150 °C for 2 h, then at 180 °C for 2 h, and finally at 200 °C for 2 h to obtain CL/GNSs-CNT/CE composites.

相比于商用的电磁屏蔽材料(20dB),实施例3制备的CL/GNSs-CNT/CE复合材料的电磁屏蔽效能为28.2dB,相应的提高了41%。Compared with the commercial electromagnetic shielding material (20dB), the electromagnetic shielding efficiency of the CL/GNSs-CNT/CE composite prepared in Example 3 is 28.2dB, a corresponding increase of 41%.

实施例4Example 4

一种CL/GNSs-CNT/CE复合材料的制备方法,具体步骤如下:A preparation method of CL/GNSs-CNT/CE composite material, the specific steps are as follows:

步骤1,将8g聚乙烯醇颗粒溶于92ml去离子水中,于90℃水浴锅中反应1~2h,得到质量浓度为80mg/ml的聚乙烯醇溶液;Step 1, dissolve 8g of polyvinyl alcohol particles in 92ml of deionized water, and react in a 90°C water bath for 1 to 2 hours to obtain a polyvinyl alcohol solution with a mass concentration of 80mg/ml;

步骤2,将7wt%石墨烯和1wt%碳纳米管分散在10ml上述聚乙烯醇溶液中,超声搅拌50min,得到石墨烯-碳纳米管/聚乙烯醇溶液;Step 2, disperse 7wt% graphene and 1wt% carbon nanotubes in 10ml of the above polyvinyl alcohol solution, and ultrasonically stir for 50min to obtain a graphene-carbon nanotube/polyvinyl alcohol solution;

步骤3,制备CL/GNSs-CNT复合材料,具体步骤如下:Step 3, prepare the CL/GNSs-CNT composite material, and the specific steps are as follows:

步骤3.1,将丝瓜络洗净,切取40×30mm大小的矩形,放置在60℃真空烘箱中烘干,将石墨烯-碳纳米管/聚乙烯醇溶液浇在丝瓜络上,使溶液均匀包裹在丝瓜络纤维上,放置在60℃真空烘箱中烘干后压实;Step 3.1, wash the loofah, cut a rectangle of size 40×30mm, place it in a 60°C vacuum oven to dry, pour the graphene-carbon nanotube/polyvinyl alcohol solution on the loofah, and make the solution evenly wrapped in the loofah. On the loofah fiber, place it in a 60°C vacuum oven to dry and compact it;

步骤3.2,将上述被压实的丝瓜放入管式炉专用的矩形船中,在均匀的氮气气氛中,1000℃下保温2h,升温速率为5℃/min,得到CL/GNSs-CNT复合材料;Step 3.2, put the above-mentioned compacted loofah into a rectangular boat dedicated to the tube furnace, and keep it at 1000 °C for 2 h in a uniform nitrogen atmosphere, with a heating rate of 5 °C/min to obtain a CL/GNSs-CNT composite material ;

步骤4,制备CL/GNSs-CNT/CE复合材料:Step 4, preparation of CL/GNSs-CNT/CE composites:

具体为:将2g氰酸酯(BADCy)和0.5g环氧树脂(E-51)在80℃下混合,搅拌30min,然后浇铸在CL/GNSs-CNT上,先于120℃的条件下固化1h,再于150℃的条件下固化2h,之后再于180℃的条件下固化2h,最后于200℃的条件下固化2h,得到CL/GNSs-CNT/CE复合材料。Specifically: mix 2g cyanate ester (BADCy) and 0.5g epoxy resin (E-51) at 80°C, stir for 30min, then cast on CL/GNSs-CNT, and cure at 120°C for 1h first , and then cured at 150 °C for 2 h, then at 180 °C for 2 h, and finally at 200 °C for 2 h to obtain CL/GNSs-CNT/CE composites.

相比于商用的电磁屏蔽材料(20dB),实施例4制备的CL/GNSs-CNT/CE复合材料的电磁屏蔽效能为30.7dB,相应的提高了53.5%。Compared with the commercial electromagnetic shielding material (20dB), the electromagnetic shielding efficiency of the CL/GNSs-CNT/CE composite prepared in Example 4 is 30.7dB, a corresponding increase of 53.5%.

实施例5Example 5

一种CL/GNSs-CNT/CE复合材料的制备方法,具体步骤如下:A preparation method of CL/GNSs-CNT/CE composite material, the specific steps are as follows:

步骤1,将8g聚乙烯醇颗粒溶于92ml去离子水中,于90℃水浴锅中反应1~2h,得到质量浓度为80mg/ml的聚乙烯醇溶液;Step 1, dissolve 8g of polyvinyl alcohol particles in 92ml of deionized water, and react in a 90°C water bath for 1 to 2 hours to obtain a polyvinyl alcohol solution with a mass concentration of 80mg/ml;

步骤2,将7wt%石墨烯和1wt%碳纳米管分散在10ml上述聚乙烯醇溶液中,超声搅拌60min,得到石墨烯-碳纳米管/聚乙烯醇溶液;Step 2, dispersing 7wt% graphene and 1wt% carbon nanotubes in 10ml of the above polyvinyl alcohol solution, and ultrasonically stirring for 60min to obtain a graphene-carbon nanotube/polyvinyl alcohol solution;

步骤3,制备CL/GNSs-CNT复合材料,具体步骤如下:Step 3, prepare the CL/GNSs-CNT composite material, and the specific steps are as follows:

步骤3.1,将丝瓜络洗净,切取40×30mm大小的矩形,放置在60℃真空烘箱中烘干,将石墨烯-碳纳米管/聚乙烯醇溶液浇在丝瓜络上,使溶液均匀包裹在丝瓜络纤维上,放置在60℃真空烘箱中烘干后压实;Step 3.1, wash the loofah, cut a rectangle of size 40×30mm, place it in a 60°C vacuum oven to dry, pour the graphene-carbon nanotube/polyvinyl alcohol solution on the loofah, and make the solution evenly wrapped in the loofah. On the loofah fiber, place it in a 60°C vacuum oven to dry and compact it;

步骤3.2,将上述被压实的丝瓜放入管式炉专用的矩形船中,在均匀的氮气气氛中,1200℃下保温2h,升温速率为5℃/min,得到CL/GNSs-CNT复合材料;Step 3.2, put the above-mentioned compacted loofah into a rectangular boat dedicated to the tube furnace, in a uniform nitrogen atmosphere, keep it at 1200 ° C for 2 hours, and the heating rate is 5 ° C/min, to obtain a CL/GNSs-CNT composite material ;

步骤4,制备CL/GNSs-CNT/CE复合材料:Step 4, preparation of CL/GNSs-CNT/CE composites:

具体为:将2g氰酸酯(BADCy)和0.5g环氧树脂(E-51)在80℃下混合,搅拌30min,然后浇铸在CL/GNSs-CNT上,先于120℃的条件下固化1h,再于150℃的条件下固化2h,之后再于180℃的条件下固化2h,最后于200℃的条件下固化2h,得到CL/GNSs-CNT/CE复合材料。Specifically: mix 2g cyanate ester (BADCy) and 0.5g epoxy resin (E-51) at 80°C, stir for 30min, then cast on CL/GNSs-CNT, and cure at 120°C for 1h first , and then cured at 150 °C for 2 h, then at 180 °C for 2 h, and finally at 200 °C for 2 h to obtain CL/GNSs-CNT/CE composites.

相比于商用的电磁屏蔽材料(20dB),实施例5制备的CL/GNSs-CNT/CE复合材料的电磁屏蔽效能为35.8dB,相应的提高了79%。Compared with the commercial electromagnetic shielding material (20dB), the electromagnetic shielding efficiency of the CL/GNSs-CNT/CE composite prepared in Example 5 is 35.8dB, a corresponding increase of 79%.

本发明制备的不同石墨烯含量下,CL/GNSs-CNT/CE复合材料的SET图,如图1所示,随着石墨烯含量的增加,屏蔽效能也随之提高;不同碳化温度下,CL/GNSs-CNT/CE复合材料的SET图,如图3所示,随着碳化温度的增加,屏蔽效能随之增加。图2与图4分别为复合材料不同填料含量与碳化温度下的SER、SEA图,可以明显看出,屏蔽机制以吸收为主,反射极小,均<5dB,CL/GNSs-CNT/CE复合材料展现出优异的电磁屏蔽性能。Under different graphene contents prepared by the present invention, the SET images of CL/ GNSs -CNT/CE composite materials are shown in Figure 1. With the increase of graphene content, the shielding effectiveness also increases; under different carbonization temperatures, the The SET images of CL/ GNSs -CNT/CE composites, as shown in Fig. 3, show that the shielding effectiveness increases with the increase of carbonization temperature. Figures 2 and 4 are the SER and SE A diagrams of the composites under different filler contents and carbonization temperatures, respectively . It can be clearly seen that the shielding mechanism is mainly absorption, and the reflection is extremely small, both <5dB, CL/GNSs-CNT/ CE composites exhibit excellent electromagnetic shielding properties.

本发明方法的作用机理为:利用三维网络结构的CL/GNSs-CNT/CE复合材料,当电磁波进入时,入射电磁波与表面由于具有优良的阻抗匹配,使得电磁波易于进入材料内部。在这种特殊的多孔结构具有密集的交联管和大量的二面角,随后,入射的电磁波通过在多孔结构内的多次反射和散射来衰减入射波,从而获得较为优异的电磁屏蔽性能。The action mechanism of the method of the invention is: using the CL/GNSs-CNT/CE composite material with a three-dimensional network structure, when the electromagnetic wave enters, the incident electromagnetic wave and the surface have excellent impedance matching, so that the electromagnetic wave can easily enter the material. In this special porous structure, which has densely cross-linked tubes and a large number of dihedral angles, the incident electromagnetic waves are then attenuated by multiple reflections and scattering within the porous structure, thereby obtaining excellent electromagnetic shielding performance.

在本发明中,制备了一种多层CL/GNSs-CNT/CE复合材料。这种复合材料三维结构的独特设计使电磁波更容易进入,在多孔结构内的多次反射和散射来衰减入射波,从而获得优异的电磁屏蔽性能。氰酸酯树脂因其极低的吸湿性、良好的力学性能、优异的抗辐射性能和优异的尺寸稳定性在各个领域的广泛应用而被选为聚合物基体。制备的复合材料在聚乙烯醇溶液中石墨烯含量为7wt%、碳纳米管含量为1wt%时,碳化温度为1200℃时,电磁屏蔽效能为35.8dB。这为制作具有一定力学性能和优异电磁屏蔽性能的电磁屏蔽材料提供了可行方案。In the present invention, a multilayer CL/GNSs-CNT/CE composite was prepared. The unique design of the three-dimensional structure of this composite material makes it easier for electromagnetic waves to enter, and multiple reflections and scattering within the porous structure attenuate the incident waves, resulting in excellent electromagnetic shielding performance. Cyanate ester resin is chosen as the polymer matrix for its extremely low hygroscopicity, good mechanical properties, excellent radiation resistance and excellent dimensional stability in a wide range of applications in various fields. When the graphene content of the prepared composite material is 7wt%, the carbon nanotube content is 1wt% in the polyvinyl alcohol solution, and the carbonization temperature is 1200°C, the electromagnetic shielding efficiency is 35.8dB. This provides a feasible solution for making electromagnetic shielding materials with certain mechanical properties and excellent electromagnetic shielding properties.

本发明一种CL/GNSs-CNT/CE复合材料的制备方法,利用高温碳化法制备得到的高效电磁屏蔽性能CL/GNSs-CNT/CE复合材料,制备过程安全环保,制备工艺简单且成本低廉,具有广泛的实用性和推广价值;本发明制备方法制备的CL/GNSs-CNT/CE复合材料,电磁屏蔽性能优异,能够满足航空航天、电子包装等领域的应用要求。The invention provides a preparation method of a CL/GNSs-CNT/CE composite material. The high-efficiency electromagnetic shielding performance CL/GNSs-CNT/CE composite material is prepared by using a high-temperature carbonization method. The preparation process is safe and environmentally friendly, and the preparation process is simple and low in cost. The invention has wide practicability and popularization value; the CL/GNSs-CNT/CE composite material prepared by the preparation method of the invention has excellent electromagnetic shielding performance and can meet the application requirements in the fields of aerospace, electronic packaging and the like.

Claims (6)

1. A preparation method of a carbonized towel gourd/graphene-carbon nanotube composite material is characterized by comprising the following specific steps:
step 1, dissolving polyvinyl alcohol particles in deionized water, and reacting in a water bath kettle at 90 ℃ for 1-2 h to obtain a polyvinyl alcohol solution with the mass concentration of 80 mg/mL;
step 2, dispersing graphene and carbon nanotubes in a polyvinyl alcohol solution, and performing ultrasonic stirring to obtain a graphene-carbon nanotube/polyvinyl alcohol solution;
step 3, preparing a carbonized towel gourd/graphene-carbon nanotube composite material;
and 4, preparing the carbonized towel gourd/graphene-carbon nanotube/cyanate resin composite material.
2. The method for preparing the carbonized luffa/graphene-carbon nanotube composite material according to claim 1, wherein in the step 2, the mass ratio of the graphene to the carbon nanotubes to the polyvinyl alcohol solution is 0.025-0.062: 0.008: 10; the stirring time is 30 min-60 min.
3. The method for preparing a carbonized luffa/graphene-carbon nanotube composite material according to claim 1, wherein in step 3, the carbonized luffa/graphene-carbon nanotube composite material is prepared by the following specific steps:
step 3.1, cleaning loofah sponge, cutting into rectangular loofah sponge with the size of 40 x 30mm, placing the rectangular loofah sponge in a vacuum oven at 60 ℃ for drying for 4h, pouring graphene-carbon nano tube/polyvinyl alcohol solution on the rectangular loofah sponge, placing the rectangular loofah sponge in the vacuum oven at 60 ℃ for drying for 4h, and then compacting;
the mass ratio of the rectangular loofah sponge to the graphene-carbon nanotube/polyvinyl alcohol solution is 3: 10;
and 3.2, putting the compacted rectangular loofah sponge into a tubular furnace for carbonization to obtain the carbonized loofah/graphene-carbon nanotube composite material.
4. The method for preparing a carbonized luffa/graphene-carbon nanotube composite material according to claim 3, wherein in step 3.2, the carbonization conditions are specifically as follows: introducing nitrogen at the speed of 50-100 mL/s, heating to 800-1200 ℃ at the speed of 5 ℃/min, preserving the heat for 2h, and cooling to room temperature.
5. The method for preparing a carbonized luffa/graphene-carbon nanotube composite material according to claim 1, wherein in the step 4, specifically: mixing cyanate and epoxy resin, stirring for 30min at 80 ℃, then casting the mixture on the carbonized towel gourd/graphene-carbon nano tube composite material, firstly curing the mixture for 1h at 120 ℃, then curing the mixture for 2h at 150 ℃, then curing the mixture for 2h at 180 ℃, and finally curing the mixture for 2h at 200 ℃ to obtain the carbonized towel gourd/graphene-carbon nano tube/cyanate resin composite material.
6. The preparation method of the carbonized loofah/graphene-carbon nanotube composite material according to claim 5, wherein the mass ratio of the cyanate ester to the epoxy resin to the carbonized loofah/graphene-carbon nanotube composite material is 4: 1: 8.
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