Preparation and properties of rigid nanoporous phenolic resin-based composites
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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为增强体、杂化酚醛树脂为基体，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复合材料(RMI/PR)。该材料具有横观各向同性，且在厚度方向有最低热导率(< 0.07 W/(m∙K))；同时，陶瓷瓦增强体中纤维与纤维之间的刚性连接，使得复合材料在Z向具有更优的抗压性能和高温尺寸稳定性。进一步研究表明，随着酚醛树脂浓度的增加，复合材料的力学、隔热以及抗烧蚀性能均明显得到提升。此类复合材料兼具了轻质-高强、烧蚀维形以及防隔热一体化的功能，在中低热流、长时有氧的复杂气动热环境中具有较好的应用前景。 复合材料沿Z向的Micro-CT三维微观结构图(a)和RMI与RMI/PR沿Z向的室温热导率(b) 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 composites (RMI/PR) are prepared via a sol-gel polymerization and ambient-pressure gradient drying using rigid mullite ceramic tile as the reinforcement and hybrid phenolic resin 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 mullite ceramic tile 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 1000oC for 300 s, the backside temperature of composites decreases from 277oC to 240oC. Under the oxy-acetylene ablation at 2000oC 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. -
图 1 莫来石陶瓷瓦(RMI)沿X/Y向(a)和Z向(b)纤维分布SEM图；烧结颈结构SEM图(c)；RMI压汞孔隙分析图(d)
Figure 1. SEM image of fiber distribution in X/Y (a) and Z (b) of mullite ceramic tile (RMI); SEM images of neck formation (c); Mercury intrusion porosimetry diagram of RMI (d)
图 2 复合材料(RMI/PR)沿Z向的Micro-CT三维微观结构图(a)；RMI/PR-30纤维与树脂结合处SEM图(b)和基体SEM图(c)；RMI/PR的孔径分布图(d)；RMI/PR在N2(e)和空气氛围(f)下的TG曲线
Figure 2. The 3 D microstructure of composites (RMI/PR) in Z from micro-CT scanning (a); SEM images of fiber/resin binding (b) and matrix (c) of RMI/PR-30; (d) Pore size distribution of RMI/PR; TG curves of RMI/PR in N2 (e) and air atmosphere (f)
图 3 RMI及RMI/PR沿Z向(a)和X/Y向(b)的压缩应力-应变曲线图；RMI及RMI/PR沿Z向(c)和X/Y向(d)的压缩强度-模量变化图
Figure 3. Compressive strength-modulus variation in Z (a) and X/Y (b) diagram of RMI and RMI/PR; Compressive stress-strain in Z (c) and X/Y (d) curse of RMI and RMI/PR
图 4 RMI处于屈服阶段的纤维(a)及粘结点SEM图(b)；RMI/PR-15分别处于弹性和屈服阶段的纤维与树脂结合处SEM图(c-d)及基体SEM图(e-f)
Figure 4. (a-b) 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
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)The room-temperature thermal conductivity in Z of RMI and RMI/PR; (b) Backside temperature response curve of RMI and RMI/PR
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SEM图(h)；RMI/PR的背部温度响应曲线(i)
Figure 6. Macrograph photo 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; Backside temperature response curve of RMI/PR (i)
图 7 RMI/PR-45烧蚀后表面物质XRD分析(a)；RMI/PR-45烧蚀后表面纤维(b)与基体EDS分析(c)
Figure 7. XRD pattern of RMI/PR-45 surface substance after ablation (a); EDS analysis of surface fiber (b) and matrix (c) of RMI/PR-45 after ablation
表 1 莫来石陶瓷瓦(RMI)和刚性纳米孔酚醛树脂基复合材料(RMI/PR)的基础物理性质
Table 1. Basic physical properties of mullite ceramic tile (RMI) and rigid nanoporous phenolic resin-based composites (RMI/PR)
Sample Bulk density/
(g·cm−3)Mass ratio of
resin / %Most probable
pore
/ nmThermal 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 2 RMI及RMI/PR的抗烧蚀性能
Table 2. The 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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