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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

刘杰, 曹宇, 钱震, 等. 刚性纳米孔酚醛树脂基复合材料的制备与性能[J]. 复合材料学报, 2023, 40(10): 5601-5610. doi: 10.13801/j.cnki.fhclxb.20221221.001
引用本文: 刘杰, 曹宇, 钱震, 等. 刚性纳米孔酚醛树脂基复合材料的制备与性能[J]. 复合材料学报, 2023, 40(10): 5601-5610. doi: 10.13801/j.cnki.fhclxb.20221221.001
LIU Jie, CAO Yu, QIAN Zhen, et al. Preparation and properties of rigid nanoporous phenolic resin-based composites[J]. Acta Materiae Compositae Sinica, 2023, 40(10): 5601-5610. doi: 10.13801/j.cnki.fhclxb.20221221.001
Citation: LIU Jie, CAO Yu, QIAN Zhen, et al. Preparation and properties of rigid nanoporous phenolic resin-based composites[J]. Acta Materiae Compositae Sinica, 2023, 40(10): 5601-5610. 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
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

Preparation and properties of rigid nanoporous phenolic resin-based composites

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

     

  • 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

    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)

    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)

    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

    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

    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

    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

    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
    下载: 导出CSV

    表  2  RMI/PR复合材料的基础物理性质

    Table  2.   Basic physical properties of RMI/PR composites

    SampleBulk 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
    下载: 导出CSV

    表  3  RMI及RMI/PR的抗烧蚀性能

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

    SampleMass ablation
    rate/(g∙s−1)
    Linear ablation
    rate/(mm∙s−1)
    RMI
    RMI/PR-15
    RMI/PR-250.0270.200
    RMI/PR-300.0250.151
    RMI/PR-400.0370.144
    RMI/PR-450.0290.081
    下载: 导出CSV
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  • 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

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