刚性纳米孔酚醛树脂基复合材料的制备与性能

刘杰; 曹宇; 钱震; 刘瑞祥; 周长灵; 潘鹤林; 张亚运; 牛波; 龙东辉

doi:10.13801/j.cnki.fhclxb.20221221.001

刚性纳米孔酚醛树脂基复合材料的制备与性能

doi: 10.13801/j.cnki.fhclxb.20221221.001

刘杰¹,
曹宇¹,
钱震¹,
刘瑞祥²,
周长灵²,
潘鹤林¹,
张亚运¹,
牛波^1, ,,
龙东辉^1, ,

1.
华东理工大学　化工学院，上海 200237
2.
山东工业陶瓷研究设计院有限公司，淄博 255000

基金项目: 国家自然科学基金(22078100；52102098)；中国博士后科学基金(2022 M711140)

详细信息

通讯作者:
牛波，博士，中级，研究方向为热防护材料与技术　E-mail: niubo@ecust.edu.cn

龙东辉，博士，教授，博士生导师，研究方向为热防护材料与技术　E-mail: longdh@ecust.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2022-11-01
- 修回日期: 2022-11-23
- 录用日期: 2022-12-02
- 网络出版日期: 2022-12-23
- 刊出日期: 2023-10-15

Preparation and properties of rigid nanoporous phenolic resin-based composites

1.
School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
2.
Shandong Research and Design Institute of Industrial CeramiCS CO., LTD., Zibo 255000, China

Funds: National Natural Science Foundation of China (22078100; 52102098); Postdoctoral Science Foundation of China (2022 M711140)

摘要

摘要: 随着我国航天工程快速发展，对热防护系统的轻量化、维形性、防热效率及长时间服役能力等提出了更加苛刻的要求。本文以刚性莫来石陶瓷瓦(RMI)为增强体、杂化酚醛树脂(PR)为基体，通过溶胶-凝胶-常压梯度干燥工艺制备出一种刚性纳米孔酚醛树脂基RMI/PR复合材料，系统研究了树脂浓度对复合材料的微观结构、力学性能、隔热性能及烧蚀性能的影响。结果表明：RMI具有明显的横观各向同性，其Z向室温热导率为0.036 W/(m∙K)。随着树脂浓度从15wt%增加到45wt%，RMI/PR的密度由0.52 g/cm³逐渐增加至0.85 g/cm³，其树脂的纳米孔径从2081 nm急剧减小至32 nm。随着树脂浓度的增加，RMI/PR室温热导率缓慢增加且均小于0.07 W/(m∙K)，但其力学性能显著得到增强且Z向压缩强度最高达20.8 MPa。当RMI/PR经过1000℃、300 s的静态加热后，其背温从277℃降低至244℃；当RMI/PR经过2000℃、30 s的氧-乙炔烧蚀后，其线烧蚀率从0.200 mm/s降低至0.081 mm/s，表明树脂浓度的增加能够显著提升复合材料的高温隔热和抗烧蚀性能。
- 热防护材料 /
- 莫来石陶瓷瓦 /
- 纳米孔酚醛树脂 /
- 力学性能 /
- 隔热性能 /
- 烧蚀性能
Abstract: With the rapid development of China's domestic space engineering, the harsher requirements are put forward for lightweight, dimensional stability, thermal protection efficiency and long service capability of the thermal protection system. Rigid nanoporous phenolic resin-based RMI/PR composites are prepared via a sol-gel polymerization and ambient-pressure gradient drying using rigid mullite ceramic tile (RMI) as the reinforcement and hybrid phenolic resin (PR) as matrix. The effects of resin concentration on the microstructure, mechanical properties, thermal insulation properties and ablative properties of the composites are systematically studied. The results show that RMI has obvious transverse isotropy, and the room-temperature thermal conductivity in the Z direction is 0.036 W/(m∙K). With the increase of the resin concentration from 15wt% to 45wt%, the density of RMI/PR increases from 0.52 g/cm³ to 0.85 g/cm³, and the most probable pore size of the resin matrix decreases sharply from 2081 nm to 32 nm. With the increase of resin concentration, the room-temperature thermal conductivity of RMI/PR increases slowly and all of them are less than 0.07 W/(m∙K), but its mechanical properties are significantly enhanced and the maximum compressive strength in the Z direction of composites is up to 20.8 MPa. After static heat insulation test at 1000℃ for 300 s, the backside temperature of composites decreases from 277℃ to 240℃. Under the oxy-acetylene ablation at 2000℃ for 30 s, the linear ablation rate of the composites is reduced from 0.200 mm/s to 0.081 mm/s, indicating that the increase of resin concentration can significantly improve the high-temperature thermal insulation properties and ablation resistance of the composites.
- thermal protection material /
- mullite ceramic tile /
- nanoporous phenolic resin /
- mechanical properties /
- thermal insulation properties /
- ablative properties

HTML全文

图 1 RMI沿X/Y向 (a) 和Z向 (b) 纤维分布SEM图像；(c) RMI烧结颈结构的SEM图像；(d) RMI压汞孔隙分析图

Figure 1. SEM images of fiber distribution in X/Y (a) and Z (b) of RMI; (c) SEM image of neck formation of RMI; (d) Mercury intrusion porosimetry diagram of RMI

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图 2 (a) RMI/PR复合材料沿Z向的Micro-CT三维微观结构图；RMI/PR-30复合材料纤维与树脂结合处SEM图像 (b) 和基体SEM图像 (c)；(d) RMI/PR复合材料的孔径分布图；RMI/PR在N₂ (e) 和空气氛围 (f) 下的TG曲线

Figure 2. (a) 3D microstructure of RMI/PR composites in Z from micro-CT scanning; SEM images of fiber/resin binding (b) and matrix (c) of RMI/PR-30 composites; (d) Pore size distribution of RMI/PR composites; TG curves of RMI/PR composites in N₂ (e) and air atmosphere (f)

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图 3 RMI及RMI/PR：Z向 (a) 和X/Y向 (b) 的压缩应力-应变曲线图；Z向 (c) 和X/Y向 (d) 的压缩强度-模量变化图

Figure 3. RMI and RMI/PR: Compressive stress-strain curves in Z (a) and X/Y (b); Compressive strength-modulus variation diagram in Z (c) and X/Y (d)

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图 4 RMI处于屈服阶段的纤维 (a) 及粘结点 (b) 的SEM图像；RMI/PR-15分别处于弹性和屈服阶段的纤维与树脂结合处的SEM图像 ((c), (d)) 及基体的SEM图像 ((e), (f))

Figure 4. SEM images of fiber (a) and bonding point (b) of RMI at yield stage; SEM images of fiber/resin binding ((c), (d)) and matrix ((e), (f)) of RMI/PR-15 at elastic and yield stage, respectively

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图 5 (a) RMI及RMI/PR沿Z向的室温热导率；(b) RMI及RMI/PR的背部温度响应曲线

Figure 5. (a) Room-temperature thermal conductivity in Z of RMI and RMI/PR; (b) Backside temperature response curves of RMI and RMI/PR

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图 6 RMI (a) 和RMI/PR ((b)~(f)) 烧蚀后宏观形貌；RMI/PR-45烧蚀后表面微观形貌 (g) 和基体 (h) 的SEM图像；(i) RMI/PR的背部温度响应曲线

Figure 6. Macrograph photos of RMI (a) and RMI/PR ((b)-(f)) after ablation; SEM images of surface microstructure (g) and matrix (h) of RMI/PR-45 after ablation; (i) Backside temperature response curves of RMI/PR

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图 7 RMI/PR-45烧蚀后表面物质的XRD图谱 (a)；RMI/PR-45烧蚀后表面纤维 (b) 与基体 (c) 的EDS分析

Figure 7. XRD patterns of RMI/PR-45 surface substance after ablation (a); EDS analysis of surface fiber (b) and matrix (c) of RMI/PR-45 after ablation

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表 1 刚性纳米孔酚醛树脂基复合材料(RMI/PR)的样品编号

Table 1. Sample number of rigid nanoporous phenolic resin matrix composites (RMI/PR)

Sample number	Mass fraction of PR/wt%
RMI/PR-15	15
RMI/PR-25	25
RMI/PR-30	30
RMI/PR-40	40
RMI/PR-45	45

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表 2 RMI/PR复合材料的基础物理性质

Table 2. Basic physical properties of RMI/PR composites

Sample	Bulk density/ (g·cm⁻³)	Mass ratio of resin/%	Most probable pore/nm	Thermal conductivity/ (W∙(m∙K)⁻¹)	Specific heat capacity/(J∙(g·K)⁻¹)
RMI	0.31	0	45000	0.036	0.70
RMI/PR-15	0.52	40	2081	0.057	1.29
RMI/PR-25	0.61	49	434	0.061	1.31
RMI/PR-30	0.67	54	121	0.065	1.32
RMI/PR-40	0.77	60	63	0.067	1.34
RMI/PR-45	0.85	64	32	0.069	1.35

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表 3 RMI及RMI/PR的抗烧蚀性能

Table 3. Ablative resistance properties of RMI and RMI/PR

Sample	Mass ablation rate/(g∙s⁻¹)	Linear ablation rate/(mm∙s⁻¹)
RMI	—	—
RMI/PR-15	—	—
RMI/PR-25	0.027	0.200
RMI/PR-30	0.025	0.151
RMI/PR-40	0.037	0.144
RMI/PR-45	0.029	0.081

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