高强度-中密度纳米孔树脂基防隔热复合材料的制备与性能

钱震; 张鸿宇; 张琪凯; 王锋; 王胜; 赵坚; 牛波; 张亚运; 龙东辉

doi:10.13801/j.cnki.fhclxb.20211223.001

高强度-中密度纳米孔树脂基防隔热复合材料的制备与性能

doi: 10.13801/j.cnki.fhclxb.20211223.001

钱震¹,
张鸿宇¹,
张琪凯²,
王锋³,
王胜³,
赵坚³,
牛波¹,
张亚运¹,
龙东辉^1, ,

1.
华东理工大学　化工学院，上海 200237
2.
北京新风航天装备有限公司，北京 100854
3.
北京电子工程总体研究所，北京 100854

基金项目: 国家自然科学基金 (22078100；52102098)；上海市青年科技人才扬帆计划 (20YF1410600)

详细信息

通讯作者:
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: 2021-11-18
- 修回日期: 2021-12-08
- 录用日期: 2021-12-11
- 网络出版日期: 2021-12-23
- 刊出日期: 2023-01-15

Preparation and properties of high strength-medium density nanoporous resin-based ablation/insulation integrated composites

1.
School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
2.
Beijing Xinfeng Machinery Factory, Beijing 100854, China
3.
Beijing Institute of Electronic System Engineering, Beijing 100854, China

Funds: National Natural Science Foundation of China (22078100; 52102098); Shanghai Sailing Program (20YF1410600)

摘要

摘要: 针对新一代航天器长时防隔热-高气动剪切的防热需求，以杂化酚醛树脂为基体、纤维布/纤维网胎逐层针刺结构为增强体，通过溶胶-凝胶工艺，制备出一种中密度-高强度-防隔热一体化的纳米孔树脂基复合材料(IPC-90)，系统研究了石英纤维(QF/IPC-90)和碳纤维(CF/IPC-90)对复合材料的微观结构、力学性能、静态隔热和烧蚀性能的影响，探讨了其在低-中-高温度下的烧蚀机制。结果表明：纤维布的引入使IPC-90具有优异的力学性能(拉伸曲强度 >120 MPa，弯曲强度 >90 MPa)；纳米孔基体和纤维网胎的引入使IPC-90在中密度(~0.95 g/cm³)下具有较低的热导率(室温热导率依次为0.089 W/(m∙K)和0.120 W/(m∙K))。在1000℃静态隔热试验中，两种材料均展现了较好的热稳定性和抗氧化性，其等效热导率分别为0.142 W/(m∙K)和0.186 W/(m∙K)。在2000℃以下氧-丙烷烧蚀试验中，QF/IPC-90和CF/IPC-90的烧蚀主要由基体热解、炭化收缩引起，其1600℃下的线烧蚀率依次为0.0208 mm/s和0.0133 mm/s；在2000℃ 以上氧-乙炔烧蚀试验中，CF/IPC-90的烧蚀由表面超高温炭化-升华主导，而QF/IPC-90则因石英纤维熔融导致其抗烧蚀性下降较为明显，两者在4.2 MW/m²下的线烧蚀率依次为0.073 mm/s和0.186 mm/s。
- 热防护材料 /
- 纳米孔基体 /
- 树脂基复合材料 /
- 石英纤维 /
- 防隔热性能 /
- 碳纤维
Abstract: To meet the extreme thermal protection requirement of new-generation spacecrafts, nanoporous resin composites (IPC-90) with medium-density, high strength and excellent ablation/insulation properties had been prepared via a sol-gel polymerization using phenolic resin as nanoporous matrix and needled fiber fabric as the reinforcement. The effects of fiber type, namely quartz fiber (QF/IPC-90) and carbon fiber (CF/IPC-90) on the microstructure, mechanical properties, static thermal insulation, and ablation properties of the composites were systematically studied. The as-prepared IPC-90 with medium density of ~0.95 g/cm³ has excellent mechanical properties with tensile strength >120 MPa and bending strength >90 MPa. Due to the introduction of nanopore resin matrix and lightweight fiber felt, the resultant IPC-90 has relatively low room-temperature thermal conductivities (0.089 W/(m∙K) for QF/IPC-90 and 0.120 W/(m∙K) for CF/IPC-90), as well as low effective thermal conductivities at 1000℃. Furthermore, the possible ablation mechanisms under different temperatures were analyzed. It is found that both QF/IPC-90 and CF/IPC-90 have low linear ablation rates under the oxygen-propane ablation test below 2000℃, which are mainly caused by resin matrix pyrolysis and shrinkage. However, under the oxy-acetylene ablation test above 2000℃, the ablation of CF/IPC-90 is dominated by ultrahigh temperature carbonation-sublimation, while the severe ablation of CF/IPC-90 is caused by the melting of quartz fiber. Under the oxy-acetylene ablation of 4.2 MW/m², the linear ablation rates of CF/IPC-90 and QF/IPC-90 are 0.073 mm/s and 0.186 mm/s, respectively, being similar to the conventional high-density phenolic composites.
- thermal protection material /
- nanoporous matrix /
- resin-based composite /
- quartz fiber /
- ablation/insulation integrated performance /
- carbon fiber

HTML全文

图 1 (a) 纤维预制体结构示意图；((b)、(c)) 石英纤维增强纳米孔酚醛树脂基复合材料(QF/IPC-90)纵向截面图与SEM图像；((d)、(e)) QF/IPC-90纤维树脂结合处和树脂基体SEM图像；(f) 纤维预制体增强纳米孔酚醛树脂基复合材料(IPC-90)孔径分布图

Figure 1. (a) Schematic diagram of fiber preform; ((b), (c)) Longitudinal section and SEM images of quartz fiber reinforced nanopore phenolic resin composite (QF/IPC-90); ((d), (e)) SEM images of fiber/resin binding and matrix of QF/IPC-90 composites; (f) Pore size distribution of fiber reinforced nanopore phenolic resin composite (IPC-90)

CF—Carbon fiber

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图 2 ((a)~(c)) IPC-90复合材料拉伸、压缩和弯曲应力-应变图；(d) IPC-90复合材料力学有限元建模方法示意图；((e)、(f)) 短纤维增强复合材料模型原始和5%应变下应力；((g)、(h)) 纤维布/短纤维增强复合材料模型原始和5%应变下应力云图

Figure 2. ((a)-(c)) Tensile, compression and bending stress-strain of IPC-90 composites; (d) Schematic diagram of mechanical finite element modeling method for IPC-90 composites; ((e), (f)) Stress contour of short fiber reinforced composite model under original and 5% strain; ((g), (h)) Stress contour of fiber sheet/short fiber reinforced composite model under original and 5% strain

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图 3 (a) IPC-90复合材料受热面温度响应曲线；((b)、(c)) QF/IPC-90受热面最终温度云图和热流密度云图；(d) IPC-90复合材料背部温度响应曲线；((e)、(f)) CF/IPC-90受热面最终温度云图和热流密度云图

Figure 3. (a) Heating surface temperature response curves of IPC-90 series composite; ((b), (c)) Final heat flux and temperature contour of QF/IPC-90 heating surface; (d) Backside temperature response curves of IPC-90 series composite; ((e), (f)) Final heat flux and temperature contour of CF/IPC-90 heating surface

NT11—Temperature (K); HEL—Heat flux (W·m⁻²)

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图 4 ((a)、(b)) QF/IPC-90静态热测试后加热面照片与SEM图像；((c)、(d)) CF/IPC-90静态热测试后加热面照片与SEM图像

Figure 4. ((a), (b)) Heating surface photo and SEM image of QF/IPC-90 after static thermal assessment; ((c), (d)) Heating surface photo and SEM image of CF/IPC-90 after static thermal assessment

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图 5 IPC-90系列复合材料烧蚀温度-线烧蚀率(R_l)曲线图 (a)、烧蚀温度-质量烧蚀率(R_m)曲线图 (b)与烧蚀温度-背温曲线图 (c)

Figure 5. Ablation temperature-linear ablation rate curves (R_l) (a), mass ablation rate (R_m) curves (b) and backside temperature curves (c) of IPC-90 series composites

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图 6 ((a)~(c)) QF/IPC-90在 1200℃下烧蚀后的宏观形貌图、表面结构和纤维SEM图像；((d)~(f)) CF/IPC-90在1200℃下烧蚀后的宏观形貌图、表面结构和纤维SEM图像；((g)~(i)) QF/IPC-90在 2000℃下烧蚀后的宏观形貌图、表面结构和纤维SEM图像；((j)~(l)) CF/IPC-90在2000℃下烧蚀后的宏观形貌图、表面纤维和基体SEM图像

Figure 6. ((a)-(c)) Macrograph photo and SEM images of surface structure and fiber of QF/IPC-90 after 1200℃ ablation; ((d)-(f)) Macrograph photo and SEM images of surface structure and fiber of CF/IPC-90 after 1200℃ ablation; ((g)-(i)) Macrograph photo and SEM images of surface structure and fiber of QF/IPC-90 after 2000℃ ablation; ((j)-(l)) Macrograph photo and SEM images of surface fiber and matrix of CF/IPC-90 after 2000℃ ablation

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图 7 (a) IPC-90在 2000℃下烧蚀后表面物质的XRD图谱；(b) QF/IPC-90 在 2000℃下烧蚀后表面基体的EDS图谱；(c) QF/IPC-90在 2000℃下烧蚀后表面纤维的EDS图谱

Figure 7. (a) XRD pattern of IPC-90 surface substance after ablation under 2000℃; (b) EDS spectrum of surface matrix of QF/IPC-90 after ablation under 2000℃; (c) EDS spectrum of surface fiber of QF/IPC-90 after ablation under 2000℃

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表 1 IPC-90的基础物理性质

Table 1. Basic physical properties of IPC-90

Composite	Bulk density/ (g∙cm⁻³)	Mass ratio of resin/wt%	Bulk density of resin/ (g·cm⁻³)	Most probable pore/nm	Porosity/%	Thermal conductivity/ (W∙(m∙K)⁻¹)	Specific heat capacity/ (J∙(g·K)⁻¹)
QF/IPC-90	0.95	52.6	0.63	43	48.1	0.089	1.10
CF/IPC-90	0.93	51.6	0.64	40	47.3	0.120	1.21

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表 2 IPC-90复合材料力学性能

Table 2. Mechanical properties of IPC-90 composites

Composite	Tensile strength in X-Y/ MPa	Tensile modulus in X-Y/ GPa	Tensile elongation at break in X-Y/%	Compressive strength in Z/MPa	Compressive modulus in Z/MPa	Bending strength in Z/MPa	Bending modulus in Z/GPa	Interlaminar shear stress/ MPa
QF/IPC-90	127.6±2.7	6.58±0.26	2.89±0.11	307.2±3.2	20.0±0.2	93.6±3.3	8.23±0.10	9.0±0.2
CF/IPC-90	131.7±8.3	18.80±0.60	1.11±0.04	414.2±8.0	26.9±2.6	113.7±3.4	14.24±0.31	11.0±0.5

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