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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