A review of aligned carbon nanotube arrays and carbon/carbon composites: fabrication, thermal conduction properties and applications in thermal management
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摘要: 现代科技的发展对热管理材料提出了更高、更迫切的需求。由于具有优异的导热性、低热膨胀系数和耐高温性，定向排列碳纳米管和炭/炭复合材料作为理想的轻质、稳定的热管理材料引起了广泛的关注。本文首先介绍了炭材料的导热机制，系统评述了垂直排列碳纳米管阵列和炭/炭复合材料的制备方法，热导率的主要影响因素以及它们在热管理中的应用。总结了材料制备-结构-性能之间的关系，并给出了提高材料导热性能的策略。最后提出了垂直排列碳纳米管阵列和炭/炭复合材料在热管理应用中面临的挑战及今后的研究方向。Abstract: The development of modern technology has posed greater and more urgent needs for thermal management materials. Aligned carbon nanotube arrays and carbon/carbon composites have aroused extensive interest as ideal lightweight and stable thermal management materials because of their low thermal expansion coefficient, excellent thermal conduction and high-temperature resistance. Here, we first review the thermal conducting mechanism of carbon materials. We then describe the general fabrication methods, the main factors affecting the thermal conductivity of aligned carbon nanotube arrays and carbon/carbon composites as well as their use in thermal management. The preparation-structure-performance relationships are outlined and the strategies for achieving high thermal conductivity are summarized. Finally, a critical consideration of the challenges and prospects in the thermal management applications of aligned carbon nanotubes and carbon/carbon composites is given.
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Figure 2. FESEM micrographs of aligned CNTs synthesized on three kinds of substrate with 7 vol% H2 at 870 °C for 1 h: non crystalline substrate (a, e) Si/SiO2 and (b, f) Al2O3 and crystalline one, (c, g, d) sapphire.[48]. (Reprinted with Permission).
Figure 3. Model describing the formation of catalytic particles and the VACNT growth process[55]. (Reprinted with Permission).
Figure 4. Schematic diagram of growth of highly dense and VA-SWCNTs using Al as barrier layer (a-d). SEM micrographs of (e) Fe catalyst, (f) as-grown SWCNTs on Fe catalyst, (g) Fe/Al catalysts, and (h) as-grown highly dense and VA-SWCNTs on Fe/Al catalysts by PECVD method[29]. (i) Schematic image of the biaxial mechanical densification method to enhance the volume fraction of VASWCNT forests. (j) Dependence of the thermal diffusivity (black closed triangles for left axis) and thermal conductivity (red opened circles for right axis) of VASWCNT forests on the volume fraction[59]. (Reprinted with Permission).
Figure 5. (a) Coatings remarkably reducing thermal contact resistance (Rc) for VACNT arrays as TIMs[62]. (b) Cu-Solder-Ti/Ni/Au-MWNTs-Ti/Ni/Au-Solder-Cu configuration and approximate thicknesses[65]. (c) Thermal resistance of transferred VACNT arrays. (d) Optical images of a CPU on a motherboard and a heat sink covered by four VACNT arrays. Temperature differences (DT) between the CPU and the heat sink as a function of time using heat sinks with contact surface roughness of (e) 2.66 and (f) 0.88 mm[23]. (Reprinted with Permission).
Figure 6. (a) Schematic diagrams of 1D and 2D C/C composites and their thermal diffusion coefficient test directions[81]. (b) Weaving process of preform architecture for 3D C/C composites[85]. (c) SEM images of a whole ribbon-shaped carbon fibers after graphitization at 2800 °C. (d) SEM images of transverse section of the highly oriented C/C composite block graphitized at 3000 °C. (e) Optical photograph of one-dimensional C/C composite block[79]. (f) SEM images of graphite fibers heat-treated at 3000 °C. (g) SEM images of transverse section of the one-dimensional cylindrical C/C composites graphitized at 3000 °C. (h) The optical photographs of the graphite fiber rods after heat treatment at 3000 °C for 15 min and peeling off the T300-3k fiber shell[82]. (Reprinted with Permission).
Table 1. Comparison of TC of C/C composites reinforced with mesophase pitch-derived carbon fibers.
Sample Graphitization temperature (°C) Density (g cm−3) Thermal conductivity (W·m−1·K−1) Refs. X Y Z 1D Thermal graph panels 3000 2.2 746 - - [75] 1D Self-adhesive sheets 2600 - 852 - - [76] 1D Self-adhesive bulks 2600 2.18 717 - - [77] 1D Carbon bulks 2800 2.2 602 - - [78] 1D Carbon bulks 3000 1.76 734 - - [80] 1D Carbon bulks 3100 1.86 896 - - [79] 1D Carbon bulks (CVI+PIP) 2300 1.9 465 - 16 [81] 3000 667 25 1D Carbon rods (ICCG + CVI) 3000 1.65 569 - - [82] 1D Carbon rods (CVI) 3000 1.72 675 - - 2D Carbon bulks 3000 2.2 460 - 70 [88] 2D Carbon bulks 3000 1.95 443 - 52 [84] 2D Carbon bulks 2300 1.92 344 193 [81] 3000 345 - 3D-FMI-222 - - 200 [86] 3D-Hercules 3D - - 345 3D-FMI A27-130 309 3D-composites (N112) 2200 2.01 248 [87] 3D-composites (N11) 2200 1.79 220 3D Carbon bulks (PIP) 3000 1.95 340 [12] 3D Carbon bulks (3CVI) 3000 1.58 116 19 [85] 3D Carbon bulks (3CVI+4LPI) 3000 1.84 235 42 
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Table 2. Comparison of thermal conductivity of C/C composites with different carbon fiber reinforcements.
Sample Fiber volume fraction (%) Density (g cm−3) Thermal conductivity (W·m−1·K−1) Refs. Parallel Perpendicular T-300/AR-120 56 1.54 80.5 6.86 [93] P-55/AR-120 55 1.57 135.5 - Ribbon fiber /AR-120 - - 148.2 213.5 P-120/Petroleum pitch 45 2.00 526 - [94] K321/Petroleum pitch 60 2.00 691 - P-130/Petroleum pitch 60 2.10 851 - T-300/Pitch A 51 1.92 253.86 74.245 [95] F-180/Pitch A 50 1.98 260.34 55.570 P-100/Pitch A 54 1.90 320.06 93.119 Composites with ribbon fiber reinforcement - 2.18 837 - [96] Composites with round fiber reinforcement - 2.12 649 -
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Table 3. Comparison of thermal conductivity of C/C composites with different carbon matrices.
Sample Fiber volume fraction (%) Density (g cm−3) Thermal conductivity (W·m−1·K−1) Refs. Perpendicular Parallel M40/Phenolic resin 25 1.51 - 37 [100] M40/Propane 25 1.45 - 42 T300/Pitch A 61 1.94 71 197 [95] T300/Pitch B 55 1.99 44 182 T300/Pitch C 62 1.85 113 204 Mesophase pitch based fiber/AR pitch - 1.74 21 734 [80] Mesophase pitch based fiber/SC pitch - 1.76 21 672 Mesophase pitch based fiber/MP pitch - 1.70 19 705 T300+T700/Coal tar pitch - 1.80 67 128 [101] T300+T700/Furfural acetone resin - 1.81 48 99 T300+T700/Natural gas - 1.75 58 118 T300+T700/Xylene - 1.77 75 148 T300/Polymer resin 31 1.68 14 152 [99] T300/AR pitch 31 1.67 33 200
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