玻璃料对Si<sub>3</sub>N<sub>4</sub>改性硼酚醛树脂复合材料高温性能及其介电性能的影响

韩朋坤; 邓宗义; 李鹏飞; 杨婷莅; 万立; 董闯; 石敏先

doi:10.13801/j.cnki.fhclxb.20220809.004

玻璃料对Si₃N₄改性硼酚醛树脂复合材料高温性能及其介电性能的影响

doi: 10.13801/j.cnki.fhclxb.20220809.004

武汉理工大学　材料科学与工程学院，武汉 430070

基金项目: 上海航天科技创新基金(SAST2018-067)

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
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- 被引次数: 0
出版历程
- 收稿日期: 2022-05-20
- 修回日期: 2022-07-20
- 录用日期: 2022-07-28
- 网络出版日期: 2022-08-09
- 刊出日期: 2023-05-15

Influence of glass frit on high temperature properties and dielectric properties of Si₃N₄ modified boron phenolic resin composites

School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China

Funds: Shanghai Aerospace Science and Technology Innovation Fund (SAST2018-067)

摘要

摘要: 为了探究助熔剂对树脂基复合材料高温性能及微观结构的影响，以低熔点玻璃料(GF)为助熔剂，Si₃N₄颗粒为耐高温陶瓷填料，采用模压工艺制备GF-Si₃N₄改性高硅氧玻璃纤维增强硼酚醛树脂复合材料(GF-Si₃N₄/BPR)，研究GF对复合材料高温性能及介电性能的影响。结果表明：引入的GF促进了复合材料表面液相的形成和陶瓷层的致密化，抑制了热氧对复合材料的进一步侵蚀，复合材料高温性能明显提高。1200℃处理后，其弯曲强度与纯树脂试样(BPR)和未添加GF的试样(Si₃N₄/BPR)相比，分别提高了81.3%和14.9%；质量烧蚀率分别降低了73.1%和55.1%。此外，在8.2 GHz下，复合材料的介电常数(ε)和损耗角正切值(tanδ)随温度的升高逐渐增大。而在800℃以上，生成的玻璃相有效遏制了树脂裂解产生的游离碳与孔洞、裂纹对材料介电性能的不利影响。所制备的复合材料具有优良的高温性能和介电性能，有望应用在高温透波领域。
- Si₃N₄ /
- 耐高温 /
- 耐烧蚀 /
- 微观结构 /
- 介电性能 /
- 可陶瓷化复合材料
Abstract: To investigate effect of flux on properties and microstructure of resin matrix composites at elevated temperature, glass frit (GF) and Si₃N₄ modified high silica glass fiber reinforced boron phenolic resin composites (GF-Si₃N₄/BPR) were prepared via a compression molding technique using low melting point GF as flux and Si₃N₄ particles as high temperature resistant fillers. The influence of GF on the high temperature properties and dielectric properties of composites was studied. The results show that the introduced GF promotes the formation of liquid phase on the surface of composites and the densification of the ceramic layer, inhibiting erosion of composites by oxygen at elevated temperatures and significantly improving the high temperature performance of composites. The flexural strength of GF-Si₃N₄/BPR treated at 1200℃ was increased by 81.3% and 14.9%, respectively, compared with high silica glass fiber reinforced boron phenolic resin composites (BPR) and Si₃N₄ modified high silica glass fiber reinforced boron phenolic resin composites (Si₃N₄/BPR), while the mass ablation rate was reduced by 73.1% and 55.1%, respectively, compared with BPR and Si₃N₄/BPR. Furthermore, at 8.2 GHz, the dielectric constant (ε) and loss tangent (tanδ) of the composites gradually increased with increasing temperature. At temperatures above 800°C, the resulting glass phase effectively restrains the adverse effects of free carbon, pores, and cracks generated by resin cracking on the dielectric properties of the material. The prepared composite material has excellent high temperature properties and dielectric properties, and is expected to be applied in the field of high temperature wave transmission.
- Si₃N₄ /
- high temperature resistance /
- ablation resistance /
- microstructure /
- dielectric properties /
- ceramizable composite

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图 1 空气气氛下GF-Si₃N₄/BPR复合材料的TG (a)和DTG (b)曲线

Figure 1. TG (a) and DTG (b) curves of GF-Si₃N₄/BPR composites in air atmosphere

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图 4 不同温度处理后Si₃N₄/BPR (a)和10GF-Si₃N₄/BPR (b)裂解产物的XRD图谱

Figure 4. XRD patterns of cracked products of Si₃N₄/BPR (a) and 10GF-Si₃N₄/BPR (b) treated at different temperatures

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图 2 不同温度处理后的GF-Si₃N₄/BPR复合材料弯曲强度

RT—Room temperature

Figure 2. Flexural strength of GF-Si₃N₄/BPR composites treated at different temperatures

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图 3 1200℃处理后GF-Si₃N₄/BPR复合材料表面和断面微观形貌：((a), (c), (e)) BPR、Si₃N₄/BPR和10GF-Si₃N₄/BPR的表面；((b), (d), (f)) BPR、Si₃N₄/BPR和10GF-Si₃N₄/BPR的断面

Figure 3. Surface and cross-section micro-morphologies of GF-Si₃N₄/BPR composites treated at 1200℃: ((a), (c), (e)) Surfaces of BPR, Si₃N₄/BPR and 10GF-Si₃N₄/BPR; ((b), (d), (f)) Cross-sections of BPR, Si₃N₄/BPR and 10GF-Si₃N₄/BPR

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图 5 1200℃处理后GF-Si₃N₄/BPR复合材料的微观形貌图及相应的元素EDS映射：(a) Si₃N₄/BPR；(b) 10GF-Si₃N₄/BPR

Figure 5. Micro-morphology of GF-Si₃N₄/BPR composites treated at 1200℃ and corresponding element EDS mapping: (a) Si₃N₄/BPR; (b) 10GF-Si₃N₄/BPR

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图 6 BPR (a)、Si₃N₄/BPR (b)和10GF-Si₃N₄/BPR (c)氧乙炔烧蚀后表面形貌

Figure 6. Surface morphologies of BPR (a), Si₃N₄/BPR (b) and 10GF-Si₃N₄/BPR (c) after oxyacetylene ablation

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图 7 GF-Si₃N₄/BPR复合材料的线烧蚀率和质量烧蚀率

Figure 7. Line and mass ablation rates of GF-Si₃N₄/BPR composites

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图 8 氧乙炔烧蚀后Si₃N₄/BPR (a)和10GF-Si₃N₄/BPR (b)表面微观形貌和EDS分析

Figure 8. Surface morphology and EDS analysis of Si₃N₄/BPR (a) and 10GF-Si₃N₄/BPR (b) after oxyacetylene ablation

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图 9 氧乙炔烧蚀后Si₃N₄/BPR和10GF-Si₃N₄/BPR表面残留物物相分析

Figure 9. Phase analysis of residues on the surface of Si₃N₄/BPR and 10GF-Si₃N₄/BPR after oxyacetylene ablation

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图 10 不同温度处理后的GF-Si₃N₄/BPR复合材料介电常数ε (a) 和介电损耗角正切tanδ (b)变化曲线

Figure 10. Variation curves of dielectric constant ε (a) and dielectric loss tangent tanδ (b) of GF-Si₃N₄/BPR composites treated at different temperatures

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图 11 GF-Si₃N₄/BPR复合材料在800℃ (a)和1400℃ (b)空气气氛下处理20 min残留物的拉曼光谱

D, G—Band peak

Figure 11. Raman spectra of residues of GF-Si₃N₄/BPR composites treated at 800℃ (a) and 1400℃ (b) in air for 20 min

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表 1 低熔点玻璃料(GF)主要成分及含量

Table 1. Main components and contents of low melting point glass frit (GF) wt%

SiO₂	K₂O	Na₂O	ZnO	Al₂O₃	BaO	TiO₂	Bi₂O₃	P₂O₅	Fe₂O₃
52.04	16.26	8.43	5.68	0.44	4.33	9.24	2.96	0.13	0.10

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表 2 GF-Si₃N₄/BPR复合材料配方

Table 2. GF-Si₃N₄/BPR composite formulations

Sample	Mass ratio
Sample	BPR	Si₃N₄	GF
BPR	100	0	0
Si₃N₄/BPR	100	30	0
5GF-Si₃N₄/BPR	100	30	5
10GF-Si₃N₄/BPR	100	30	10
15GF-Si₃N₄/BPR	100	30	15
20GF-Si₃N₄/BPR	100	30	20
Note: BPR—Boron phenolic resin.

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表 3 GF-Si₃N₄/BPR复合材料的热分解特性

Table 3. Thermal decomposition properties of GF-Si₃N₄/BPR composites

Sample	T_max/℃	Residue yield/%
Sample	T_max/℃	400℃	600℃	800℃	1200℃	1400℃
BPR	495.9	90.63	54.32	52.88	52.15	51.54
Si₃N₄/BPR	494.2	92.41	69.73	69.14	68.98	68.87
5GF-Si₃N₄/BPR	501.3	93.42	70.21	69.24	69.33	68.75
10GF-Si₃N₄/BPR	481.8	93.30	71.05	71.40	71.56	70.54
15GF-Si₃N₄/BPR	500.9	94.33	75.14	75.31	75.40	73.91
20GF-Si₃N₄/BPR	495.7	93.28	73.73	74.36	74.78	73.61
Note: T_max—Temperature at which the thermal mass loss rate is the maximum.

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表 4 不同温度处理后的GF-Si₃N₄/BPR复合材料电导率

Table 4. Conductivity of GF-Si₃N₄/BPR composites treated at different temperatures

Sample	Conductivity/(10⁻¹⁰ S·m^–1)
Sample	RT	800℃	1000℃	1200℃	1400℃
BPR	0.222	113	93.5	162	358
Si₃N₄/BPR	0.125	149	142	80	188
10GF-Si₃N₄/BPR	0.111	87	150	65.8	128

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表 5 GF-Si₃N₄/BPR复合材料裂解玻璃碳的I_D/I_G值

Table 5. I_D/I_G values of pyrolyzed glassy carbon of GF-Si₃N₄/BPR composites

Sample	I_D/I_G
Sample	800℃	1400℃
BPR	2.717	2.403
Si₃N₄/BPR	3.236	2.364
10GF-Si₃N₄/BPR	3.663	2.326
Note: I_D/I_G—Intensity ratio of the D band to the G band.

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参考文献(26)

[1]	朱召贤, 朱小飞, 黄洪勇, 等. 低密度树脂基防热材料研究进展[J]. 中国材料进展, 2019, 38(11):1086-1092. doi: 10.7502/j.issn.1674-3962.201806008 ZHU Zhaoxian, ZHU Xiaofei, HUANG Hongyong, et al. Research progress of low-density resin based thermal protection materials[J]. Materials China,2019,38(11):1086-1092(in Chinese). doi: 10.7502/j.issn.1674-3962.201806008
[2]	张瑾瑜, 雷豹, 杨东生, 等. 航天飞行器典型高温透波结构热匹配性能分析[J]. 宇航总体技术, 2021, 5(3):59-64. ZHANG Jinyu, LEI Bao, YANG Dongsheng, et al. The analysis of thermal matching of a typical high temperature wave transmission structure of aero-spacecraft[J]. Astronautical Systems Engineering Technology,2021,5(3):59-64(in Chinese).
[3]	TRIANTOU K, PEREZ B, MARINOU A, et al. Performance of cork and ceramic matrix composite joints for reentry thermal protection structures[J]. Composites Part B: Engineering,2017,108:270-278.
[4]	傅华东, 秦岩, 王辉, 等. 2.5D 石英纤维增强硼酚醛树脂可陶瓷化复合材料的制备与烧蚀性能[J]. 复合材料学报, 2020, 3(4):767-774. FU Huadong, QIN Yan, WANG Hui, et al. Preparation and ablation performance of 2.5D fiber reinforced boron-phenolic resin ceramizable composites[J]. Acta Materiae Compositae Sinica,2020,3(4):767-774(in Chinese).
[5]	任粒. 聚合物基功能复合材料的设计、制备及介电和磁性能研究[D]. 北京: 北京科技大学, 2016. REN Li. Design and preparation of polymer based functional composites with dielectric and magnetic preperties[D]. Beijing: University of Science and Technology Beijing, 2016(in Chinese).
[6]	TANG L, ZHANG J L, TANG Y S, et al. Polymer matrix wave transparent composites: A review[J]. Journal of Materials Science & Technology,2021,75(16):225-251.
[7]	宋麦丽, 傅利坤. 高性能耐高温陶瓷透波材料的研究进展[J]. 材料导报, 2012, 26(S1):226-229. SONG Maili, FU Likun. Research development of high temperature ceramic wave-transparent materials[J]. Materials Reports,2012,26(S1):226-229(in Chinese).
[8]	黄良, 朱朋莉, 梁先文, 等. 无机颗粒填充聚合物复合材料的介电性能研究[J]. 材料导报, 2014, 28(19):11-20. HUANG Liang, ZHU Pengli, LIANG Xianwen, et al. Study on the dielectric properties of inorganic particles filled polymer composites[J]. Materials Reports,2014,28(19):11-20(in Chinese).
[9]	BADHE Y, BALASUBRAMANIAN K. Novel hybrid ablative composites of resorcinol formaldehyde as thermal protection systems for reentry vehicles[J]. RSC Advances,2014,4(55):28956-28963.
[10]	YANG W, XU B, QI M, et al. Improving ablation properties of ceramifiable vitreous silica fabric reinforced boron phenolic resin composites via an incurporation of MoSi₂[J]. Plastics, Rubber and Composites,2020,49(10):456-469. doi: 10.1080/14658011.2020.1808758
[11]	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):2673-2681. 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):2673-2681(in Chinese). doi: 10.13801/j.cnki.fhclxb.20210628.001
[12]	石毓锬, 梁国正, 兰立文. 树脂基复合材料在导弹雷达天线罩中的应用[J]. 材料工程, 2000(5):36-39. SHI Yutan, LIANG Guozheng, LAN Liwen. Research of polymer-matrix composites for missile radomes[J]. Jour-nal of Materials Engineering,2000(5):36-39(in Chinese).
[13]	宋麦丽, 崔红, 闫联生, 等. 高硅氧/有机硅透波材料介电性能实验分析[J]. 固体火箭技术, 2006(5):364-366, 371. SONG Maili, CUI Hong, YAN Liansheng, et al. Experimental analysis on dielectric properties of silica glass/silicone radome material[J]. Journal of Solid Rocket Technology,2006(5):364-366, 371(in Chinese).
[14]	王思青, 张长瑞, 王圣威, 等. Si₃N₄基复相陶瓷天线罩材料的制备及性能[J]. 国防科技大学学报, 2006(2):44-47. doi: 10.3969/j.issn.1001-2486.2006.02.010 WANG Siqing, ZHANG Changrui, WANG Shengwei, et al. Preparation and properties of Si₃N₄ matrix radome ceramics[J]. Journal of National University of Defense Technology,2006(2):44-47(in Chinese). doi: 10.3969/j.issn.1001-2486.2006.02.010
[15]	QI G J, ZHANG C R, HU H F, et al. Preparation of three-dimensional silica fiber reinforced silicon nitride compo-sites using perhydropolysilazane as precursor[J]. Materials Letters,2005,59(26):3256-3258. doi: 10.1016/j.matlet.2005.04.057
[16]	中国国家标准化管理委员会. 纤维增强塑料弯曲性能试验方法: GB/T 1449—2005[S]. 北京: 中国标准出版社, 2005. Standardization Administration of the People’s Republic of China. Test method for bending properties of fiber reinforced plastics: GB/T 1449—2005[S]. Beijing: China Standard Press, 2005(in Chinese).
[17]	国防科学技术工业委员会. 烧蚀材料烧蚀试验方法: GJB 323 A—1996[S]. 北京: 中国标准出版社, 1996. Commission of Scientific and Technical Industry on National Defence. Ablation test method for ablation materials: GJB 323 A—1996[S]. Beijing: China Standard Press, 1996(in Chinese).
[18]	范珊珊, 石敏先, 孟盼, 等. 助熔剂对陶瓷化硼酚醛复合材料热行为及微观结构的影响[J]. 复合材料学报, 2017, 34(1):60-66. doi: 10.13801/j.cnki.fhclxb.20160411.004 FAN Shanshan, SHI Minxian, MENG Pan, et al. Effects of fusing agent on the thermal behavior and microstructure of ceramifiable boron phenolic resin composites[J]. Acta Materiae Compositae Sinica,2017,34(1):60-66(in Chinese). doi: 10.13801/j.cnki.fhclxb.20160411.004
[19]	ZHANG L, ZHANG Y, WANG L, et al. Phenolic resin modified by boron-silicon with high char yield[J]. Polymer Testing,2019,73:208-213. doi: 10.1016/j.polymertesting.2018.11.033
[20]	徐博, 丁杰, 王兵, 等. AlB₂对高硅氧纤维增强可瓷化酚醛树脂基复合材料及其裂解产物力学性能的影响[J]. 复合材料学报, 2021, 38(1):129-136. XU Bo, DING Jie, WANG Bing, et al. Effects of AlB₂ on mechanical properties of high silica fiber reinforced ceramicizable phenolic resin matrix composites and their pyrolysis products[J]. Acta Materiae Compositae Sinica,2021,38(1):129-136(in Chinese).
[21]	邢建申, 王树彬, 张跃. 石英纤维析晶行为[J]. 复合材料学报, 2006(6): 75-79. XING Jianshen,WANG Shubin, ZHANG Yue. Crystallization of quartz fiber[J]. Acta Materiae Compositae Sinica, 2006(6): 75-79(in Chinese).
[22]	SHI M X, CHEN X, FAN S S, et al. Fluxing agents on ceramification of composites of MgO-Al₂O₃-SiO₂/boron phenolic resin[J]. Journal of Wuhan University of Technology,2018,33(2):381-388. doi: 10.1007/s11595-018-1833-8
[23]	闵春英, 黄玉东, 刘丽, 等. 温度对甲基硅树脂基复合材料介电性能及力学性能的影响[J]. 固体火箭技术, 2007(4):348-352. doi: 10.3969/j.issn.1006-2793.2007.04.020 MIN Chunying, HUANG Yudong, LIU Li, et al. Effect of temperature on dielectric and mechanical properties of methyl silicone resin composites[J]. Journal of Solid Rocket Technology,2007(4):348-352(in Chinese). doi: 10.3969/j.issn.1006-2793.2007.04.020
[24]	詹未荫. 聚合物基微波介质复合材料的制备与性能[D]. 武汉: 武汉理工大学, 2014. ZHAN Weiyin. Preparation and properties of microwave dielectric polymer matrix composites[D]. Wuhan: Wuhan University of Technology, 2014(in Chinese).
[25]	涂建华, 张利波, 彭金辉, 等. 酚醛树脂基玻璃炭结构的显微激光拉曼光谱研究[J]. 高分子材料科学与工程, 2005(6):205-208. doi: 10.3321/j.issn:1000-7555.2005.06.052 TU Jianhua, ZHANG Libo, PENG Jinhui, et al. Microscopic laser Raman spectroscopy of phenolic resinbased glass carbon structure[J]. Polymeric Materials Science and Engineering,2005(6):205-208(in Chinese). doi: 10.3321/j.issn:1000-7555.2005.06.052
[26]	WANG S, YONG W, CHENG B, et al. The thermal stability and pyrolysis mechanism of boron-containing phenolic resins: The effect of phenyl borates on the char formation[J]. Applied Surface Science,2015,331:519-529. doi: 10.1016/j.apsusc.2015.01.062