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石榴石微粉改性硼酚醛树脂的制备与耐高温性能

董闯 邓宗义 任依林 唐青秀 黄志雄 石敏先

董闯, 邓宗义, 任依林, 等. 石榴石微粉改性硼酚醛树脂的制备与耐高温性能[J]. 复合材料学报, 2022, 39(6): 2698-2706. doi: 10.13801/j.cnki.fhclxb.20210628.001
引用本文: 董闯, 邓宗义, 任依林, 等. 石榴石微粉改性硼酚醛树脂的制备与耐高温性能[J]. 复合材料学报, 2022, 39(6): 2698-2706. doi: 10.13801/j.cnki.fhclxb.20210628.001
DONG Chuang, DENG Zongyi, REN Yilin, et al. Preparation and high temperature resistance of modified boron phenolic resin with almandine micropowder[J]. Acta Materiae Compositae Sinica, 2022, 39(6): 2698-2706. doi: 10.13801/j.cnki.fhclxb.20210628.001
Citation: DONG Chuang, DENG Zongyi, REN Yilin, et al. Preparation and high temperature resistance of modified boron phenolic resin with almandine micropowder[J]. Acta Materiae Compositae Sinica, 2022, 39(6): 2698-2706. doi: 10.13801/j.cnki.fhclxb.20210628.001

石榴石微粉改性硼酚醛树脂的制备与耐高温性能

doi: 10.13801/j.cnki.fhclxb.20210628.001
基金项目: 上海航天科技创新基金(SAST2018-067);中央高校基本科研业务费专项资金(2021-zy-001)
详细信息
    通讯作者:

    石敏先,博士,教授,博士生导师,研究方向为聚合物基复合材料 E-mail:minxianshi@whut.edu.cn

  • 中图分类号: TB332

Preparation and high temperature resistance of modified boron phenolic resin with almandine micropowder

  • 摘要: 针对纤维增强酚醛树脂复合材料耐热性不足、抗烧蚀性能差的问题,采用岛状硅酸盐矿物-石榴石微粉(AM)作为可陶瓷化填料来改性硼酚醛树脂(BPR),采用模压工艺制备不同填料含量的AM/BPR可陶瓷化复合材料及高硅氧玻璃纤维(HSF)-AM/BPR可陶瓷化复合材料,探究AM对BPR体系的耐热、耐烧蚀和力学性能的影响及在不同温度下材料的物相转变及微观形貌变化。结果表明,随着AM含量的提高,AM/BPR复合材料的耐热性提高,800℃以上形成液相,并在1100℃时形成较致密的陶瓷层,对复合材料高温性能、抗烧蚀性能提高有重要作用,当AM含量为50wt%时,线烧蚀率为0.221 mm/s,质量烧蚀率为0.103 g/s,与纯BPR相比分别降低了44.05%和43.6%;当AM含量为40wt%时,HSF-AM/BPR可陶瓷化复合材料高温处理前后的弯曲强度比未加填料前分别提高了29%和47.97%,其优良的耐热、耐烧蚀和力学性能有望作为热防护材料应用于航天领域。

     

  • 图  1  不同AM含量的AM/BPR可陶瓷化复合材料的TG (a) 和DTG (b) 曲线

    Figure  1.  TG (a) and DTG (b) curves of AM/BPR ceramizable composites with different AM contents

    图  2  不同AM含量的AM/BPR可陶瓷化复合材料的线烧蚀率和质量烧蚀率

    Figure  2.  Linear ablation rate and mass ablation rate of AM/BPR ceramizable composites with different AM contents

    图  3  氧乙炔烧蚀后AM/BPR可陶瓷化复合材料表面的微观形貌、EDS分析 (a) 及XRD图谱 (b)

    Figure  3.  Surface micromorphology, EDS analysis (a) and XRD pattarns (b) of AM/BPR ceramizable composites surface after oxyacetylene ablation

    图  4  不同温度处理后的AM/BPR可陶瓷化复合材料的微观形貌

    Figure  4.  Micromorphologies of AM/BPR ceramizable composites treated at different temperatures ((a) Room temperature; (b) 800℃; (c) 1 000℃; (d) 1 100℃; (e) 1 200℃)

    图  5  不同温度处理过后AM/BPR可陶瓷化复合材料表面残留物相的XRD图谱

    Figure  5.  XRD spectra of residual phases on the surface of AM/BPR ceramizable composites treated at different temperatures

    图  6  不同AM含量的HSF-AM/BPR可陶瓷化复合材料的弯曲强度

    Figure  6.  Flexural strength of HSF-AM/BPR ceramizable composites with different AM contents

    图  7  AM含量为0wt% (a) 和40wt% (b) 的HSF-AM/BPR可陶瓷化复合材料断面的微观形貌(常温)

    Figure  7.  Micromorphologies of the cross-section of HSF-AM/BPR ceramizable composites with 0wt% (a) and 40wt% (b) of AM (Room temperature)

    图  8  1200℃高温处理20 min后不同AM含量的HSF-AM/BPR可陶瓷化复合材料的表面形貌变化(AM含量从左向右依次是0wt%、20wt%、30wt%、40wt%和50wt%)

    Figure  8.  Surface morphology change of HSF-AM/BPR ceramizable composites with different AM contents after high temperature treatment at 1200℃ for 20 min (Content of AM is 0wt%, 20wt%, 30wt%, 40wt% and 50wt% from left to right)

    图  9  AM含量为0wt% ((a)~(b)) 和40wt% ((c)~(d)) 的HSF-AM/BPR可陶瓷化复合材料的表面与断面的微观形貌(1200℃、20 min)

    Figure  9.  Micromorphologies of the surface and section of HSF-AM/BPR ceramizable composites with 0wt% ((a)-(b)) and 40wt% ((c)-(d)) of AM (1200℃, 20 min)

    表  1  石榴石微粉(AM)/硼酚醛树脂(BPR)可陶瓷化复合材料配方(wt%)

    Table  1.   Formula of almandine micropowder (AM)/boron phenolic resin (BPR) ceramizable composites (wt%)

    SampleBPRAM
    1 100 0
    2 80 20
    3 70 30
    4 60 40
    5 50 50
    6 40 60
    下载: 导出CSV

    表  2  AM/BPR可陶瓷化复合材料的热分解特性

    Table  2.   Thermal decomposition characteristics of AM/BPR ceramizable composites

    Mass fraction of
    AM/wt%
    Tmax/℃
    Residue yield(Carbon fixation amount)/%
    350℃800℃1200℃1450℃
    0 666.54 87.43(−) 16.43(−) 9.19(−) 6.19(−)
    20 696.04 93.81(3.87) 35.36(2.22) 32.37(4.69) 30.00(4.89)
    30 577.97 94.45(3.25) 40.55(−0.95) 40.54(3.61) 38.96(4.40)
    40 663.16 95.03(2.58) 48.53(−1.33) 48.49(2.32) 46.55(2.53)
    50 542.92 97.23(3.52) 63.38(5.17) 63.94(8.52) 62.77(9.29)
    60 646.28 97.41(2.44) 66.88(0.31) 67.78(3.11) 67.26(4.32)
    Notes: Tmax—Temperature at which the rate of thermal mass loss is maximum;
    Carbon fixation amount—Difference between the actual residue yield and the theoretical residue yield.
    下载: 导出CSV
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出版历程
  • 收稿日期:  2021-05-12
  • 修回日期:  2021-06-09
  • 录用日期:  2021-06-18
  • 网络出版日期:  2021-06-28
  • 刊出日期:  2022-06-01

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