热管理用高导热碳化硅陶瓷基复合材料研究进展

doi:10.15541/jim20220640

摘要/Abstract

摘要：

碳化硅陶瓷基复合材料以其高比强度、高比模量、高导热、良好的耐烧蚀性能、高温抗氧化性、抗热震性能等特性, 广泛应用于航空航天、摩擦制动、核聚变等领域, 成为先进的高温结构及功能材料。本文综述了高导热碳化硅陶瓷基复合材料制备及性能等方面的最新研究进展。引入高导热相, 如金刚石粉、中间相沥青基碳纤维等用以增强热输运能力; 优化热解炭炭与碳化硅基体界面用以降低界面热阻; 热处理用以获得结晶度更高、导热性能更好的碳化硅基体; 设计预制体结构用以建立连续导热通路等方法, 提高碳化硅陶瓷基复合材料的热导率。此外, 本文展望了高导热碳化硅陶瓷基复合材料后续研究方向, 即综合考虑影响碳化硅陶瓷基复合材料性能要素, 优化探索高效、低成本的制备工艺; 深入分析高导热碳化硅陶瓷基复合材料导热机理, 灵活运用复合材料结构与性能的构效关系, 以期制备尺寸稳定、具有优异热物理性能的各向同性高导热碳化硅陶瓷基复合材料。

关键词: 热管理, 高导热, 碳化硅, 复合材料, 综述

Abstract:

Silicon carbide ceramic matrix composites have been widely used in aerospace, friction brake, fusion fields and so on, and become advanced high-temperature structural and functional composites, due to their high specific strength and specific modulus, excellent ablation and oxidation resistance, and high conductivity and good thermal shock resistance. This paper reviews the latest research progress in preparation and property of silicon carbide ceramics matrix composites (CMCs) with high thermal conductivity. Researchers have improved the thermal conductivity of silicon carbide CMCs, including by introducing highly thermal conductive phases for reinforcing heat transport, such as diamond powders, and mesophase pitch-based carbon fibers (MPCF), by optimizing the interface between pyrolytic carbon (PyC) and silicon carbide matrix for reducing interfacial thermal resistance, by heat-treating for obtaining silicon carbide matrix with higher crystallinity and better thermal conductivity, and by designing preform structure for establishing continuous thermal conduction path. Meanwhile, research interests on silicon carbide CMCs are to explore new preparation with high efficiency and low cost through optimising their influencing factors, and to obtain isotropic highly thermal conductivity with dimensional stability and physical properties through deep understanding their thermal conductive mechanism, and flexible method based on the structure-activity relationship.

Key words: thermal management, high thermal conductivity, silicon carbide, composite, review

中图分类号:

TB332

陈强, 白书欣, 叶益聪. 热管理用高导热碳化硅陶瓷基复合材料研究进展[J]. 无机材料学报, 2023, 38(6): 634-646.

CHEN Qiang, BAI Shuxin, YE Yicong. Highly Thermal Conductive Silicon Carbide Ceramics Matrix Composites for Thermal Management: a Review[J]. Journal of Inorganic Materials, 2023, 38(6): 634-646.

图/表 15

表1 碳化硅陶瓷纤维性能及产品[21]

Table 1 Properties and products of silicon carbide based fibers[21]

Producer	Brand	Modulus/GPa	Strength/MPa	Density/(g·cm^-3)	Diameter/μm	TC/(W·m^-1·K^-1)
Nicalon	NL202	220	3000	2.55	14	2.97
	Hi-Nicalon	270	2800	2.74	12	7.77
	Hi-Nicalon-S	420	2600	3.05	12	18.4
Tyranno	Lox M	187	3300	2.48	11	1.4
	ZMI	200	3400	2.48	11	2.5
	SA	380	2800	3.10	10/7.5	65
Sylramic	Sylramic	400	2800	3.05	10	40-45
Sylramic	Sylramic-iBN	400	3200	3.10	10	>46
KD^[33]	KD-A	170	2100	2.43	12.3	-
	KD-B	300	3000	2.76	11.2
	KD-C	320	2800	2.87	11.1

图1 不同金刚石的硅-金刚石-碳化硅复合材料显微组织及热导率[31]

Fig. 1 Microstructures and thermal conductivities of Si-diamond-SiC composites with different diamond volume contents[31] (a) Si-20% diamond (sintered at 1523 K); (b) Si-60% diamond (sintered at 1643 K); (c) Fracture surface of (b); (d) EDX of(c); (e) XRD patterns of (a, b); (f) Experimental and theoretical thermal conductivity of Si-diamond-SiC composites

图2 不同体积分数的金刚石-碳化硅复合材料显微组织及热导率[32]

Fig. 2 Microstructures and thermal conductivities of diamond/SiC composites with different diamond volume contents[32] (a) RBSD1; (b) RBSD2; (c) RBSD3; (d) RBSD4; (e) Diamond/SiC interface; (f) Graphite interlayer in diamond/SiC interfacial region; (g) TEM image of diamond/SiC interfacial region in post-annealing RBSD; (h) Thermal conductivities of RBSDs before and after high temperature annealing

表2 沥青基碳纤维性能及产品[42-43]

Table 2 Properties and products of pitch based carbon fibers[42-43]

Producer	Brand	Modulus/GPa	Strength/MPa	Density/(g·cm^-3)	Diameter/μm	TC/(W·m^-1·K^-1)
UCC	P75	517	2100	2.00	10	185
	P100	759	2410	2.15	10	520
	P-120	828	2410	2.18	10	640
Mitsubishi	K-1100	931	3100	2.2	10	1000
	K13D2U	935	3700	2.21	10	800
	K13C2U	900	3800	2.2	10	620
	K63B12	860	2600	2.15	10	400
Nippon	Granoc	920	3530	2.19	7	600
	YS-95A	920	3530	2.19	7	600
	Granoc	880	3530	2.18	7	500
	YS-90A	880	3530	2.18	7	500
NOCVARB	NM6030-15	≥550	≥1500	≥2.1	-	≥250
	NM9050-20	≥850	≥2000	≥2.15	-	≥450
	NM9080-20	≥850	≥2000	≥2.15	-	≥750
	NMA080-25	≥950	≥2500	≥2.15	-	≥750
TIANCE-TECH	TC-HC-600-S	750	2300	2.20	13	600
ECO	-	500-900	2500-3500	2.2	8-12	500-800
TOYI-CARBEN	TYG-1	800	2300	2.2	12	600
TOYI-CARBEN	TYG-2	900	2500	2.2	12	800

图3 3D HTC C/C-SiC制备工艺及微观组织[25]

Fig. 3 Diagram of fabrication and microstructure of the 3D HTC C/C-SiC composite[25] (a) Fabrication process of 3D HTC C/C-SiC; (b-f) Microstructures of the 3D HTC C/C-SiC composite; (g) Interface energy spectrum diagram of the 3D HTC C/C-SiC; (h) Ablation tests and (i) temperature curves of the C/C-SiC

图4 烧蚀后的碳纤维增强碳化硅陶瓷基复合材料表面形貌[47]

Fig. 4 Surface topographies of the as-ablated C/C-SiC[47] (a) Image of the as-ablated C/C-SiC; (b-d) Magnification images of (b) middle region, (c) area “A” and (d) naked fibers in the center region of (a)

图5 C/C-SiC复合材料制备工艺流程图[48]

Fig. 5 Flow diagram of preparation process of the C/C-SiC composite[48]

图6 碳化硅纤维表面电泳沉积碳纳米管微观组织及复合材料热物理性能[57]

Fig. 6 Microstructures of SiC fiber with electrodeposited CNTs and thermophysical properties of SiCf/SiC compersites[57] (a) Surface of SiC fibers with CNTs; (b) Surface of SiC fibers without CNTs; (c) Interface between CNTs and PyC; (d) TEM image of PyC deposited on CNTs; (e, f) HRTEM images of PyC deposited on (e) SiC fibers and (f) CNTs; (g) Bending strength and (h) thermal conductivity of SiC/SiC composites with different interfaces

图7 Cpf/SiC复合材料(1600 ℃-2 h)热处理(a)前(b)后的热导率[48]

Fig. 7 Thermal conductivities of Cpf/SiC composites (a) before and (b) after heat-treatment(1600 ℃-2 h)[48]

图8 金刚石/SiC复合材料界面区域表征[58]

Fig. 8 Characterization of diamond/SiC interfacial zone[58] (a) TEM image of diamond and SiC separated by a layer of graphite with lighter contrast; (b) HRTEM image of the rectangular region in (a) showing the graphite (G) and diamond (D) zones; (c-e) TEM and HRTEM images of (c, d) graphite layer and (e) reaction formed nano-crystalline SiC with stacking faults; (f) TEM image of Al4C3 formed adjacent to the interface; (g) HRTEM image from the rectangular region in (f); (h) ADF STEM of diamond/SiC interfacial area in (f)

图9 不同温度热处理的SiCf/SiC复合材料微观组织及热导率[59]

Fig. 9 Microstructures and thermal conductivities of SiCf/SiC composites with different heat-treatment[59] (a) SiC matrix without heat-treatment; (b) SiC matrix with 1700 ℃-2 h heat-treatment; (c) SiC matrix with 1900 ℃-2 h heat-treatment; (d-f) TEM images of SiC matrix corresponding to (a-c); (g) Thermal conductivity of 2D SiCf/SiC after different heat-treatments; (h) Full width at half maximum of (111) diffraction crystal plane after different heat-treatments

图10 含石墨烯-碳纤维增强碳化硅陶瓷基复合材料导热通路设计[61]

Fig. 10 Design of heat conductive channels of Cf/SiC with well-designed graphene[61]

图11 含微管道的三维高导热碳纤维增强碳化硅陶瓷基复合材料结构设计[62]

Fig. 11 Structural design of three-dimensional-linked Cf/SiC with micro-pipelines[62]

图12 生长30 min的 (a, b) ECNT-CF和(c, d) VACNT-CF不同放大倍率的微观组织[52]

Fig. 12 Low and high magnification SEM images of (a, b) ECNT-CF and (c, d) VACNT-CF fabrics with a growth duration of 30 min[52]

图13 定向碳纳米管-碳纤维增强碳化硅陶瓷基复合材料结构设计[63]

Fig. 13 Structure design of the Cf/SiC with aligned carbon nanotube[63]

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