CN104961464A - Carbon-based composite with high rebound resilience and high heat conductivity coefficient along thickness direction and preparation method of carbon-based composite - Google Patents
Carbon-based composite with high rebound resilience and high heat conductivity coefficient along thickness direction and preparation method of carbon-based composite Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 92
- 239000010439 graphite Substances 0.000 claims abstract description 92
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 34
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 34
- HAILJWAVHOQKGZ-UHFFFAOYSA-N cyclopenta-1,3-diene iron(2+) methane Chemical compound C.[Fe++].c1cc[cH-]c1.c1cc[cH-]c1 HAILJWAVHOQKGZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000006835 compression Effects 0.000 claims abstract description 10
- 238000007906 compression Methods 0.000 claims abstract description 10
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 48
- 238000007731 hot pressing Methods 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 3
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- 238000010438 heat treatment Methods 0.000 description 6
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- 239000007770 graphite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010063493 Premature ageing Diseases 0.000 description 1
- 208000032038 Premature aging Diseases 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种沿厚度方向同时具有高回弹性和高导热系数碳基复合材料的制备方法，膨胀石墨中的石墨片层被阵列碳纳米管连接，石墨片层之间的空隙被阵列碳纳米管填充；沿厚度方向导热系数≧25W/(m·K)；压缩10％后回弹率≧90％。利用二茂铁碳源溶液生长阵列碳纳米管，二茂铁裂解成铁原子并附着在膨胀石墨的石墨片层，碳源溶液裂解成碳原子并吸附在铁原子表面，从而在膨胀石墨的石墨片层间生长出阵列碳纳米管，利用碳纳米管的高导热性能实现膨胀石墨中石墨层间热流的传递，石墨片层会沿垂直热压方向即水平方向取向，阵列碳纳米管在厚度方向连接和填充膨胀石墨的片层和空隙，获得沿厚度方向具有高回弹性和高导热系数碳基复合材料。
The invention relates to a preparation method of a carbon-based composite material with high resilience and high thermal conductivity along the thickness direction. The graphite sheets in expanded graphite are connected by arrayed carbon nanotubes, and the gaps between graphite sheets are arrayed by carbon nanotubes. Tube filling; thermal conductivity ≧25W/(m·K) along the thickness direction; rebound rate ≧90% after 10% compression. The ferrocene carbon source solution is used to grow arrayed carbon nanotubes. Ferrocene is cracked into iron atoms and attached to the graphite sheets of expanded graphite. The carbon source solution is cracked into carbon atoms and adsorbed on the surface of iron atoms, so that the graphite Arrays of carbon nanotubes are grown between the sheets, and the high thermal conductivity of carbon nanotubes is used to realize the transfer of heat flow between graphite layers in expanded graphite. Connect and fill the sheets and voids of expanded graphite to obtain a carbon-based composite material with high resilience and high thermal conductivity along the thickness direction.
Description
技术领域technical field
本发明涉及一种沿厚度方向同时具有高弹性和高导热系数碳基复合材料的制备方法，具体地说是一种膨胀石墨和阵列碳纳米管复合材料的制备方法。The invention relates to a method for preparing a carbon-based composite material with high elasticity and high thermal conductivity along the thickness direction, in particular to a method for preparing a composite material of expanded graphite and arrayed carbon nanotubes.
背景技术Background technique
随着科学技术的快速发展，高效的导热和散热成为热管理领域的关键问题。例如随着计算机、手机等电器装置电子元件集成度的不断提高，其单位面积电子器件不断提高的发热量使系统产生的热量骤增。如果没有充分的热管理保障，极易导致相关器件提前老化或是损坏。许多电子部件需要在40～60℃的温度下才能正常工作，这对导热材料提出了越来越高的要求。传统的金属导热材料(如铝、铜等)由于存在密度较大、比热导率(热导系数与材料体积密度之比)较低、热膨胀系数较高、易氧化等局限性，已很难满足目前日益增长的散热需求。碳材料具有较高的导热系数、较低的密度以及较好的耐化学腐蚀性，是近年来最具发展前景的一类导热材料，因而在能源、通讯、电子等领域具有广阔的应用前景。With the rapid development of science and technology, efficient heat conduction and heat dissipation have become key issues in the field of thermal management. For example, with the continuous improvement of the integration of electronic components in electrical devices such as computers and mobile phones, the continuous increase in the heat generated by the electronic devices per unit area has caused a sudden increase in the heat generated by the system. If there is no adequate thermal management guarantee, it is very easy to cause premature aging or damage of related devices. Many electronic components need to work normally at a temperature of 40-60 ° C, which puts forward higher and higher requirements for thermal conductive materials. Traditional metal heat-conducting materials (such as aluminum, copper, etc.) have been difficult due to the limitations of high density, low specific thermal conductivity (ratio of thermal conductivity to material volume density), high thermal expansion coefficient, and easy oxidation. To meet the current growing demand for heat dissipation. Carbon materials have high thermal conductivity, low density, and good chemical corrosion resistance. They are the most promising type of thermal conductivity materials in recent years. Therefore, they have broad application prospects in energy, communication, electronics and other fields.
膨胀石墨是由天然鳞片石墨经过插层、膨胀得到的一种疏松多孔的蠕虫状物质。膨胀石墨由于具有规整大块的石墨化壁层，声子传导的阻碍较少，导热效率很高，因而利用膨胀石墨制备碳基高导热材料成为人们的研究重点，也出现类似专利的授权或公开。中华人民共和国国家知识产权局授权号为CN101407322B、CN100368342C、CN101458049A等发明专利公布了利用压缩膨胀石墨制备导热板的技术。Expanded graphite is a loose and porous worm-like substance obtained by intercalation and expansion of natural flake graphite. Due to the regular and large graphitized wall layer of expanded graphite, there are less obstacles to phonon conduction and high thermal conductivity. Therefore, the use of expanded graphite to prepare carbon-based high thermal conductivity materials has become the focus of research, and similar patents have also been authorized or published. . The invention patents such as CN101407322B, CN100368342C, and CN101458049A issued by the State Intellectual Property Office of the People's Republic of China disclose the technology of utilizing compressed expanded graphite to prepare heat conducting plates.
以上所述的发明专利仅仅披露了传统的膨胀石墨制备方法和压制工艺，只获得了导热各向异性的石墨导热材料，并且材料的压缩回弹性较差。对于石墨片层，碳原子的晶格震动是材料导热的基础，因此石墨材料中声子传递只能沿着石墨晶面进行高速传导，而对于石墨晶面层间由于距离过远，严重影响声子的传导。在经过石墨压制工艺处理后，石墨晶面在热压作用下沿平面方向取向，因而在石墨导热片中只有在沿平面方向上具有高导热系数(大于100W/(m·K))，而沿厚度方向导热系数很低，不到10W/(m·K)(Zhi-Hai Feng,Tong-Qi Li,Zi-Jun Hu,Gao-Wen Zhao,Jun-Shan Wang,Bo-Yun Huang,Low cost preparation of high thermal conductivitycarbon blocks with ultra-high anisotropy from a commercial graphite paper,Carbon,2012,50(10):3947–3948.)。中国的专利申请CN100368342C、CN103539111A等公布的石墨导热板的沿厚度方向导热系数都在10W/(m·K)以下，压缩回弹性较差。因此，现有已公开的发明专利所获得石墨材料沿厚度方向的压缩回弹性及导热系数远不能满足高集成电子器件对导热材料导热能力的要求，在碳材料已有优势基础上开发一种沿厚度方向具有高回弹性和高导热系数的材料显得尤为重要。The above-mentioned invention patents only disclose the traditional preparation method and pressing process of expanded graphite, and only anisotropic graphite heat-conducting materials are obtained, and the compression resilience of the materials is poor. For graphite flakes, the lattice vibration of carbon atoms is the basis of material heat conduction, so the phonon transmission in graphite materials can only be conducted at high speed along the graphite crystal plane, and the distance between graphite crystal plane layers is too far, which seriously affects the sound quality. child conduction. After the graphite pressing process, the graphite crystal plane is oriented along the plane direction under the action of hot pressing, so in the graphite heat conduction sheet, only the plane direction has high thermal conductivity (greater than 100W/(m·K)), while along the The thermal conductivity in the thickness direction is very low, less than 10W/(m K) (Zhi-Hai Feng,Tong-Qi Li,Zi-Jun Hu,Gao-Wen Zhao,Jun-Shan Wang,Bo-Yun Huang,Low cost preparation of high thermal conductivitycarbon blocks with ultra-high anisotropy from a commercial graphite paper, Carbon,2012,50(10):3947–3948.). Chinese patent applications CN100368342C, CN103539111A and other graphite heat conducting plates have thermal conductivity along the thickness direction below 10W/(m·K), and the compression resilience is relatively poor. Therefore, the compression resilience and thermal conductivity of graphite materials obtained in the existing published invention patents along the thickness direction are far from meeting the requirements of highly integrated electronic devices for the thermal conductivity of thermally conductive materials. Materials with high resilience and high thermal conductivity in the thickness direction are particularly important.
发明内容Contents of the invention
本发明针对现有膨胀石墨制备的石墨导热片沿厚度方向导热系数过低及回弹性差的缺陷，提供一种沿厚度方向具有高回弹性和高导热系数的碳基复合材料及其制备方法。沿厚度方向导热系数达到25W/(m·K)，压缩10％后回弹率大于等于90％的碳基复合材料，如图1所示。The invention aims at the defects of low thermal conductivity along the thickness direction and poor resilience of the existing graphite heat conducting sheet prepared from expanded graphite, and provides a carbon-based composite material with high resilience and high thermal conductivity along the thickness direction and a preparation method thereof. The thermal conductivity along the thickness direction reaches 25W/(m·K), and the carbon-based composite material has a rebound rate greater than or equal to 90% after being compressed by 10%, as shown in Figure 1.
本发明采用以下技术方案：The present invention adopts following technical scheme:
一种沿厚度方向具有高回弹性和高导热系数的碳基复合材料；膨胀石墨中的石墨片层被阵列碳纳米管连接，石墨片层之间的空隙被阵列碳纳米管填充；沿厚度方向导热系数≧25W/(m·K)；压缩10％后回弹率≧90％。A carbon-based composite material with high resilience and high thermal conductivity along the thickness direction; graphite sheets in expanded graphite are connected by arrayed carbon nanotubes, and the gaps between graphite sheets are filled by arrayed carbon nanotubes; along the thickness direction Thermal conductivity≧25W/(m·K); rebound rate≧90% after 10% compression.
本发明的一种沿厚度方向具有高回弹性和高导热系数的碳基复合材料的制备方法，步骤如下：A method for preparing a carbon-based composite material with high resilience and high thermal conductivity along the thickness direction of the present invention, the steps are as follows:
(1)将无水乙醇与二甲苯按质量比0.1～10：1搅拌混合均匀制备碳源溶液，将二茂铁溶于上述碳源溶液，配置质量分数1～5％的二茂铁碳源溶液；(1) Stir and mix absolute ethanol and xylene at a mass ratio of 0.1 to 10:1 to prepare a carbon source solution, dissolve ferrocene in the above carbon source solution, and configure a ferrocene carbon source with a mass fraction of 1 to 5% solution;
(2)将膨胀率为100～300的膨胀石墨放置于管式炉中，通入氩气保护，加热管式炉升温至700～900℃，将二茂铁碳源溶液注射入管式炉中用以在膨胀石墨上生长阵列碳纳米管；(2) Place expanded graphite with an expansion rate of 100-300 in a tube furnace, pass through argon protection, heat the tube furnace to 700-900°C, and inject the ferrocene carbon source solution into the tube furnace Used to grow arrayed carbon nanotubes on expanded graphite;
(3)将生长阵列碳纳米管的膨胀石墨置于石墨模具中，置于真空热压炉进行高温热压，升温速度控制在200～300℃/h，热压温度为1500～2000℃，热压压力为5～40MPa，保温保压时间为0.5～1h，待温度降至100℃卸压取出样品。(3) Put the expanded graphite for growing arrayed carbon nanotubes into a graphite mold, and place it in a vacuum hot-press furnace for high-temperature hot-pressing. The compression pressure is 5-40MPa, and the heat preservation and pressure holding time is 0.5-1h. When the temperature drops to 100°C, the pressure is released and the sample is taken out.
所述步骤(2)中，二茂铁碳源溶液的注射速度为10～30mL/h，生长时间为30～120min，生长结束在惰性气体的保护下冷却至室温取出。In the step (2), the injection speed of the ferrocene carbon source solution is 10-30mL/h, the growth time is 30-120min, and the growth is completed and cooled to room temperature under the protection of an inert gas to take out.
具体说明如下：The specific instructions are as follows:
(1)膨胀石墨为一种蠕虫状的石墨材料；膨胀率是指可膨胀石墨膨胀后与膨胀前体积比；可以直接采用市售产品；(1) Expanded graphite is a worm-like graphite material; expansion rate refers to the volume ratio of expandable graphite after expansion to that before expansion; commercially available products can be directly used;
(2)二茂铁碳源溶液的作用是用于生长阵列碳纳米管，在高温管式炉中二茂铁裂解成铁原子并附着在膨胀石墨的石墨片层，碳源溶液裂解成碳原子并吸附在铁原子表面，从而在膨胀石墨的石墨片层间生长出阵列碳纳米管，如图2；(2) The role of the ferrocene carbon source solution is to grow arrayed carbon nanotubes. In the high-temperature tube furnace, the ferrocene is cracked into iron atoms and attached to the graphite sheet of expanded graphite, and the carbon source solution is cracked into carbon atoms. And adsorbed on the surface of iron atoms, so that carbon nanotube arrays grow between the graphite sheets of expanded graphite, as shown in Figure 2;
(3)生长在膨胀石墨的石墨片层间的阵列碳纳米管主要作用是利用碳纳米管的高导热性能实现膨胀石墨中石墨层间热流的传递，具体说，如图1和2，垂直生长于膨胀石墨片层的阵列碳纳米管，，连接膨胀石墨的石墨片层，填充石墨片层之间的空隙，由于碳纳米管沿管轴方向具有极高的导热系数(～2000W/(m·K))，密集排列的阵列碳纳米管在膨胀石墨的石墨片层之间提供大量导热通道，使得膨胀石墨的石墨片层之间的热流可通过层间的阵列碳纳米管传递，进而提高膨胀石墨的石墨片层之间的导热系数，同时由于高密度的阵列碳纳米管填充了膨胀石墨的石墨片层之间的空隙，进而提高了其压缩回弹性；(3) The main function of the arrayed carbon nanotubes grown between graphite sheets of expanded graphite is to utilize the high thermal conductivity of carbon nanotubes to realize the transfer of heat flow between graphite layers in expanded graphite. Specifically, as shown in Figures 1 and 2, vertical growth The carbon nanotubes in the array of expanded graphite sheets are connected to the graphite sheets of expanded graphite to fill the gaps between the graphite sheets. Since the carbon nanotubes have a very high thermal conductivity along the tube axis (~2000W/(m· K)), the densely arranged array carbon nanotubes provide a large number of heat conduction channels between the graphite sheets of expanded graphite, so that the heat flow between the graphite sheets of expanded graphite can be transferred through the arrayed carbon nanotubes between the layers, thereby improving the expansion The thermal conductivity between the graphite sheets of graphite, and because the high-density array carbon nanotubes fill the gaps between the graphite sheets of expanded graphite, thereby improving its compression resilience;
(4)在热压条件下，膨胀石墨的石墨片层会沿垂直热压方向即水平方向取向，此时阵列碳纳米管在厚度方向连接和填充膨胀石墨的片层和空隙，进而获得沿厚度方向具有高回弹性和高导热系数碳基复合材料。(4) Under hot-pressing conditions, the graphite sheets of expanded graphite will be oriented along the vertical hot-pressing direction, that is, the horizontal direction. At this time, the arrayed carbon nanotubes connect and fill the sheets and voids of expanded graphite in the thickness direction, thereby obtaining Orientation carbon matrix composites with high resilience and high thermal conductivity.
通过以上步骤的阵列碳纳米管在膨胀石墨的石墨层间的生长及热压成型，实现了高导热阵列碳纳米管对膨胀石墨的石墨片层的连接和空隙的填充，得到沿厚度方向导热系数大于等于25W/(m·K)，压缩10％后回弹率大于等于90％的碳基复合材料。Through the growth of arrayed carbon nanotubes between the graphite layers of expanded graphite and hot-press forming through the above steps, the connection of the arrayed carbon nanotubes to the graphite sheets of expanded graphite and the filling of the gaps are realized, and the thermal conductivity along the thickness direction is obtained. A carbon-based composite material greater than or equal to 25W/(m·K), with a rebound rate greater than or equal to 90% after compression of 10%.
本发明的有益效果：本发明的基体原料膨胀石墨易得，阵列碳纳米管的生长形态可控。本发明中碳基复合材料微观结构有序化和致密化可高效完成，可获得沿厚度方向具有高回弹性和高导热系数的碳基复合材料，其沿厚度方向的回弹性及导热能力远远优于传统的膨胀石墨热压卷材以及其他膨胀石墨和碳纳米管复合材料。Beneficial effects of the present invention: the matrix raw material expanded graphite of the present invention is easy to obtain, and the growth form of the arrayed carbon nanotubes is controllable. In the present invention, the ordering and densification of the microstructure of the carbon-based composite material can be efficiently completed, and a carbon-based composite material with high resilience and high thermal conductivity along the thickness direction can be obtained, and its resilience and thermal conductivity along the thickness direction are much higher. Superior to traditional expanded graphite hot-pressed coils and other expanded graphite and carbon nanotube composites.
附图说明：Description of drawings:
图1为本发明的碳基复合材料的微观示意图；Fig. 1 is the microcosmic schematic diagram of carbon-based composite material of the present invention;
图2为阵列碳纳米管在膨胀石墨层间生长的扫描电镜图片。Fig. 2 is a scanning electron microscope picture of arrayed carbon nanotubes growing between expanded graphite layers.
具体实施方式Detailed ways
下面给出本发明的实施例,是对本发明的进一步说明，而不是限制本发明的范围。Provide the embodiment of the present invention below, be further description of the present invention, rather than limit the scope of the present invention.
实施例1Example 1
选取无水乙醇与二甲苯分别1.8g与18g配置成碳源溶液，在碳源溶液中加入0.2g二茂铁配置成质量分数1％的二茂铁碳源溶液。将膨胀率为100的膨胀石墨放置于管式炉中，通入氩气保护，加热管式炉升温至700℃，注射上述二茂铁碳源溶液，所述二茂铁碳源溶液的注射速度控制在10mL/h，生长时间为120min，生长结束后停止注入二茂铁碳源溶液，并在惰性气体的保护下冷却至室温取出。将生长阵列碳纳米管的膨胀石墨置于石墨模具中，置于真空热压炉进行高温热压，升温速度为200℃/h，热压温度为1500℃，热压压力为5MPa，保温保压0.5h，待温度降至100℃卸压取出样品。测试样品沿厚度方向导热系数为25W/(m·K)，将样品沿厚度方向压缩10％后回弹率为95％。Select 1.8 g and 18 g of absolute ethanol and xylene respectively to prepare a carbon source solution, and add 0.2 g of ferrocene to the carbon source solution to prepare a ferrocene carbon source solution with a mass fraction of 1%. Place expanded graphite with an expansion rate of 100 in a tube furnace, pass through argon protection, heat the tube furnace to 700°C, inject the above-mentioned ferrocene carbon source solution, and the injection speed of the ferrocene carbon source solution is The growth time was controlled at 10mL/h, and the growth time was 120min. After the growth, stop injecting the ferrocene carbon source solution, and take it out after cooling to room temperature under the protection of inert gas. The expanded graphite with carbon nanotubes growing arrays is placed in a graphite mold and placed in a vacuum hot-press furnace for high-temperature hot-pressing. The heating rate is 200°C/h, the hot-pressing temperature is 1500°C, and the hot-pressing pressure is 5MPa. After 0.5h, when the temperature drops to 100°C, release the pressure and take out the sample. The thermal conductivity of the test sample along the thickness direction is 25W/(m·K), and the rebound rate is 95% after the sample is compressed by 10% along the thickness direction.
实施例2Example 2
选取无水乙醇与二甲苯各9.5g配置成碳源溶液，在碳源溶液中加入1g二茂铁配置成质量分数5％的二茂铁碳源溶液。将膨胀率为300的膨胀石墨放置于管式炉中，通入氩气保护，加热管式炉升温至900℃，注射上述二茂铁碳源溶液，所述二茂铁碳源溶液的注射速度控制在30mL/h，生长时间为30min，生长结束后停止注入二茂铁碳源溶液，并在惰性气体的保护下冷却至室温取出。将生长阵列碳纳米管的膨胀石墨置于石墨模具中，置于真空热压炉进行高温热压，升温速度为300℃/h，热压温度为2000℃，热压压力为40MPa，保温保压1h，待温度降至100℃卸压取出样品。测试样品沿厚度方向导热系数为35W/(m·K)，将样品沿厚度方向压缩10％后回弹率为98％。9.5 g of absolute ethanol and xylene were selected to form a carbon source solution, and 1 g of ferrocene was added to the carbon source solution to form a ferrocene carbon source solution with a mass fraction of 5%. Place expanded graphite with an expansion rate of 300 in a tube furnace, pass through argon protection, heat the tube furnace to 900°C, inject the above-mentioned ferrocene carbon source solution, and the injection speed of the ferrocene carbon source solution is Control at 30mL/h, growth time is 30min, stop injecting ferrocene carbon source solution after growth, and cool to room temperature under the protection of inert gas to take out. The expanded graphite growing arrayed carbon nanotubes is placed in a graphite mold and placed in a vacuum hot-press furnace for high-temperature hot-pressing. The heating rate is 300°C/h, the hot-pressing temperature is 2000°C, and the hot-pressing pressure is 40MPa. After 1h, when the temperature dropped to 100°C, the pressure was released and the sample was taken out. The thermal conductivity of the test sample along the thickness direction is 35W/(m·K), and the rebound rate is 98% after the sample is compressed by 10% along the thickness direction.
实施例3Example 3
选取无水乙醇与二甲苯各9.6g配置成碳源溶液，在碳源溶液中加入0.8g二茂铁配置成质量分数4％的二茂铁碳源溶液。将膨胀率为200的膨胀石墨放置于管式炉中，通入氩气保护，加热管式炉升温至800℃，注射上述二茂铁碳源溶液，所述二茂铁碳源溶液的注射速度控制在20mL/h，生长时间为60min，生长结束后停止注入二茂铁碳源溶液，并在惰性气体的保护下冷却至室温取出。将生长阵列碳纳米管的膨胀石墨置于石墨模具中，置于真空热压炉进行高温热压，升温速度为260℃/h，热压温度为1600℃，热压压力为30MPa，保温保压0.6h，待温度降至100℃卸压取出样品。测试样品沿厚度方向导热系数为27W/(m·K)，将样品沿厚度方向压缩10％后回弹率为90％。9.6 g of absolute ethanol and xylene were selected to form a carbon source solution, and 0.8 g of ferrocene was added to the carbon source solution to form a ferrocene carbon source solution with a mass fraction of 4%. Place expanded graphite with an expansion rate of 200 in a tube furnace, pass through argon protection, heat the tube furnace to 800°C, inject the above-mentioned ferrocene carbon source solution, and the injection speed of the ferrocene carbon source solution is The growth time was controlled at 20mL/h, and the growth time was 60min. After the growth, stop injecting the ferrocene carbon source solution, and take it out after cooling to room temperature under the protection of inert gas. The expanded graphite with carbon nanotubes growing arrays is placed in a graphite mold, placed in a vacuum hot-press furnace for high-temperature hot-pressing, the heating rate is 260°C/h, the hot-pressing temperature is 1600°C, and the hot-pressing pressure is 30MPa. After 0.6h, when the temperature drops to 100°C, release the pressure and take out the sample. The thermal conductivity of the test sample along the thickness direction is 27W/(m·K), and the rebound rate is 90% after the sample is compressed by 10% along the thickness direction.
实施例4Example 4
选取无水乙醇与二甲苯分别18g与1.8g配置成碳源溶液，在碳源溶液中加入0.2g二茂铁配置成质量分数1％的二茂铁碳源溶液。将膨胀率为100的膨胀石墨放置于管式炉中，通入氩气保护，加热管式炉升温至750℃，注射上述二茂铁碳源溶液，所述二茂铁碳源溶液的注射速度控制在15mL/h，生长时间为50min，生长结束后停止注入二茂铁碳源溶液，并在惰性气体的保护下冷却至室温取出。将生长阵列碳纳米管的膨胀石墨置于石墨模具中，置于真空热压炉进行高温热压，升温速度为200℃/h，热压温度为1800℃，热压压力为30MPa，保温保压0.8h，待温度降至100℃卸压取出样品。测试样品沿厚度方向导热系数为26W/(m·K)，将样品沿厚度方向压缩10％后回弹率为98％。18g and 1.8g of absolute ethanol and xylene were respectively selected to form a carbon source solution, and 0.2g of ferrocene was added to the carbon source solution to form a ferrocene carbon source solution with a mass fraction of 1%. Place expanded graphite with an expansion rate of 100 in a tube furnace, pass through argon protection, heat the tube furnace to 750°C, inject the above-mentioned ferrocene carbon source solution, and the injection speed of the ferrocene carbon source solution is Control at 15mL/h, growth time is 50min, stop injecting ferrocene carbon source solution after growth, and cool to room temperature under the protection of inert gas to take out. The expanded graphite with carbon nanotubes growing arrays is placed in a graphite mold, placed in a vacuum hot-press furnace for high-temperature hot-pressing, the heating rate is 200°C/h, the hot-pressing temperature is 1800°C, and the hot-pressing pressure is 30MPa. After 0.8h, when the temperature drops to 100°C, release the pressure and take out the sample. The thermal conductivity of the test sample along the thickness direction is 26W/(m·K), and the rebound rate is 98% after the sample is compressed by 10% along the thickness direction.
实施例5Example 5
选取无水乙醇与二甲苯各9.8g配置成碳源溶液，在碳源溶液中加入0.4g二茂铁配置成质量分数2％的二茂铁碳源溶液。将膨胀率为200的膨胀石墨放置于管式炉中，通入氩气保护，加热管式炉升温至750℃，注射上述二茂铁碳源溶液，所述二茂铁碳源溶液的注射速度控制在15mL/h，生长时间为60min，生长结束后停止注入二茂铁碳源溶液，并在惰性气体的保护下冷却至室温取出。将生长阵列碳纳米管的膨胀石墨置于石墨模具中，置于真空热压炉进行高温热压，升温速度为280℃/h，热压温度为2000℃，热压压力为30MPa，保温保压1h，待温度降至100℃卸压取出样品。测试样品沿厚度方向导热系数为32W/(m·K)，将样品沿厚度方向压缩10％后回弹率为95％。9.8 g of absolute ethanol and xylene were selected to form a carbon source solution, and 0.4 g of ferrocene was added to the carbon source solution to form a ferrocene carbon source solution with a mass fraction of 2%. Place expanded graphite with an expansion rate of 200 in a tube furnace, pass through argon protection, heat the tube furnace to 750°C, inject the above-mentioned ferrocene carbon source solution, and the injection speed of the ferrocene carbon source solution is The growth time was controlled at 15mL/h, and the growth time was 60min. After the growth, stop injecting the ferrocene carbon source solution, and take it out after cooling to room temperature under the protection of inert gas. The expanded graphite with carbon nanotube growth arrays is placed in a graphite mold, placed in a vacuum hot-press furnace for high-temperature hot-pressing, the heating rate is 280°C/h, the hot-pressing temperature is 2000°C, and the hot-pressing pressure is 30MPa. After 1h, when the temperature dropped to 100°C, the pressure was released and the sample was taken out. The thermal conductivity of the test sample along the thickness direction is 32W/(m·K), and the rebound rate is 95% after the sample is compressed by 10% along the thickness direction.
实施例6Example 6
选取无水乙醇与二甲苯各9.5g配置成碳源溶液，在碳源溶液中加入1g二茂铁配置成质量分数5％的二茂铁碳源溶液。将膨胀率为100的膨胀石墨放置于管式炉中，通入氩气保护，加热管式炉升温至700℃，注射上述二茂铁碳源溶液，所述二茂铁碳源溶液的注射速度控制在20mL/h，生长时间为60min，生长结束后停止注入二茂铁碳源溶液，并在惰性气体的保护下冷却至室温取出。将生长阵列碳纳米管的膨胀石墨置于石墨模具中，置于真空热压炉进行高温热压，升温速度为200℃/h，热压温度为2000℃，热压压力为35MPa，保温保压1h，待温度降至100℃卸压取出样品。测试样品沿厚度方向导热系数为36W/(m·K)，将样品沿厚度方向压缩10％后回弹率为96％。9.5 g of absolute ethanol and xylene were selected to form a carbon source solution, and 1 g of ferrocene was added to the carbon source solution to form a ferrocene carbon source solution with a mass fraction of 5%. Place expanded graphite with an expansion rate of 100 in a tube furnace, pass through argon protection, heat the tube furnace to 700°C, inject the above-mentioned ferrocene carbon source solution, and the injection speed of the ferrocene carbon source solution is The growth time was controlled at 20mL/h, and the growth time was 60min. After the growth, stop injecting the ferrocene carbon source solution, and take it out after cooling to room temperature under the protection of inert gas. The expanded graphite with carbon nanotubes growing arrays is placed in a graphite mold and placed in a vacuum hot-press furnace for high-temperature hot-pressing. The heating rate is 200°C/h, the hot-pressing temperature is 2000°C, and the hot-pressing pressure is 35MPa. After 1h, when the temperature dropped to 100°C, the pressure was released and the sample was taken out. The thermal conductivity of the test sample along the thickness direction is 36W/(m·K), and the rebound rate is 96% after the sample is compressed by 10% along the thickness direction.
本发明公开和提出的沿厚度方向同时具有高弹性和高导热系数碳基复合材料的制备方法，本领域技术人员可通过借鉴本文内容，适当改变原料和工艺路线等环节实现，尽管本发明的方法和制备技术已通过较佳实施例子进行了描述，相关技术人员明显能在不脱离本发明内容、精神和范围内对本文所述的方法和技术路线进行改动或重新组合，来实现最终的制备技术。特别需要指出的是，所有相类似的替换和改动对本领域技术人员来说是显而易见的，他们都被视为包括在本发明精神、范围和内容中。The preparation method of carbon-based composite materials with high elasticity and high thermal conductivity along the thickness direction disclosed and proposed by the present invention can be realized by those skilled in the art by referring to the content of this article and appropriately changing the raw materials and process routes. Although the method of the present invention and preparation techniques have been described through preferred implementation examples, and those skilled in the art can obviously modify or recombine the methods and technical routes described herein without departing from the content, spirit and scope of the present invention to realize the final preparation techniques . In particular, it should be pointed out that all similar substitutions and modifications will be obvious to those skilled in the art, and they are all considered to be included in the spirit, scope and content of the present invention.
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| CN106276859A (en) * | 2016-08-15 | 2017-01-04 | 天津大学 | A kind of preparation method of the CNT microsphere being coated with carbon film |
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