通过与苯乙烯共聚改善含硅芳炔树脂及其复合材料性能

杨娜; 苏韬; 黄锴荻; 王文俊

通过与苯乙烯共聚改善含硅芳炔树脂及其复合材料性能

杨娜¹,
苏韬²,
黄锴荻¹,
王文俊^1, ,

1.
北京理工大学　材料科学与工程学院, 北京 100081
2.
中国航空工业集团济南特种结构研究所, 济南 250023

详细信息

通讯作者:
王文俊，博士，副教授，硕士生导师，研究方向为聚合物基复合材料　E-mail: wangwenjun@bit.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: 2022-10-18
- 修回日期: 2022-11-17
- 录用日期: 2022-12-06
- 网络出版日期: 2022-12-22

Modification of silicon-containing arylacetylene resin and its composite properties by copolymerization with styrene

1.
School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
2.
Jinan Institute of Special Structures, Aviation Industry Corporation of China, Jinan 250023, China

摘要

摘要: 含硅芳炔树脂(PSA)/石英纤维(QF)复合材料是一种新型耐高温透波材料，在航空航天领域具有广阔的应用前景。但由于PSA树脂质脆、极性低，加上石英纤维表面光滑，导致两者间界面粘结弱，突出表现为复合材料层间性能(如层间剪切强度)低，成为限制其应用的瓶颈问题。本文采用一种简便低成本的路径，使苯乙烯(ST)与PSA树脂共聚，通过降低树脂体系的交联密度，达到降低树脂脆性、进而提高复合材料层间剪切强度的目的。这种改性方法的优势体现在：ST不会影响树脂的固化规律和工艺；随着苯乙烯添加量的增加，改性PSA树脂的耐热性有所降低，但其T_d5均接近500℃，仍具有良好的耐热性；其次，改性后的复合材料保持了良好的介电性能，ε为3.09，tan δ为2×10^-3；复合材料在保持较高弯曲强度的同时，层间剪切强度得到显著提升。当ST添加量为15%时，QF/PSA-15ST复合材料在室温下的层间剪切强度提高了53.0%，350℃下提高了98.3%；350℃下层间剪切强度保留率为78.3%，高于改性前的60.4%。1QF/PSA复合材料改性前后的力学性能
- 含硅芳炔树脂 /
- 复合材料 /
- 苯乙烯 /
- 增韧 /
- 层间剪切强度
Abstract: Quartz fiber (QF) reinforced poly (silica-containing arylacetylene) (PSA) composite is a new type of highly promising new wave-transparent materials with highly heat-resistance. However, the brittleness and low molecular polarity of PSA resins, combined with the smooth surface of quartz fibers, results in a weak interfacial adhesion, and low interlaminar shear strength (ILSS) of the composites. In this paper, silicon-containing arylacetylene resin was modified by copolymerizing with styrene (ST). As a consequence, the crosslinking density was decreased, the crosslinking network got homogenized, and the crack resistance of the resin against load was improved. Finally, the ILSS of Quartz fiber reinforced PSA composites was improved. The properties of the resin and composites were characterized with differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), mechanical property testing, dielectric property testing, rheological property testing. The results showed that the addition of ST didn’t affect the curing process of the resin. With the increase of ST content, the heat resistance of modified PSA resin decreased to some extent, but its T_d5 was still close to 500℃, which was much higher than the expected application temperature of 350℃. The modified composite also maintained the good dielectric properties with dielectric constant of 3.09 and tan δ of 0.002. The results also showed that the addition of ST significantly improved ILSS. For instance, the ILSS of QF/PSA-15ST increased by 53.0% at room temperature and 98.3% at 350℃. Compared with that at room temperature, the retention rate of interlaminar shear strength at 350℃ was 78.3%, which was much higher than that before modification (60.4% ).
- silicon-containing arylacetylene resin /
- composites /
- styrene /
- toughening /
- interlaminar shear strength (ILSS)

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1 MDPES的结构式

1. The structural formula of MDPES

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图 1 添加不同比例苯乙烯(ST)的MDPES树脂的DSC曲线

Figure 1. DSC curves of MDPES resin with different ratio of styrene (ST)

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2 MDPES的固化机制

2. Curing mechanism of MDPES

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图 2 PSA0 和PSA15的流变行为

Figure 2. Rheology behaviors of PSA0 and PSA15

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图 3 添加不同比例ST的MDPES树脂固化物在N₂中的TGA(a)和DTG(b)曲线；分别在空气(c)和在氮气(d)中350℃下恒温30 min的热重曲线

Figure 3. TGA and DTG curves (a),(b) of the cured MDPES resin adding with different ratio of Styrene in N₂ ; thermostatic TG at 350℃ for 30 min in air (c) and N₂ (d).

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图 4 QF/PSA复合材料改性前后的DMA曲线

Figure 4. DMA curves of QF/PSA composites before and after modification

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图 5 QF/PSA复合材料改性前后的DSC曲线

Figure 5. DSC curves of QF/PSA composites before and after modification

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图 6 QF/PSA复合材料改性前后的力学性能

Figure 6. Mechanical properties of QF/PSA composites before and after modification

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图 7 改性前(a)后(b)树脂浇注体断面的SEM图

Figure 7. SEM images of resin castings before and after modification (a) (b)

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图 8 短梁弯曲实验后复合材料层合板的CT图

Figure 8. CT image of composite laminate after short beam bending test

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图 9 短梁弯曲载荷示意图

Figure 9. Illustration of short beam shear loading

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表 1 添加不同比例ST的MDPES树脂的DSC数据

Table 1. DSC data of MDPES resin adding with different ratio of styrene

	T_i /℃	T_p /℃	T_f /℃	ΔH/(J·g⁻¹)
PSA0	210.6	257.7	334.7	196.5
PSA10	206.1	257.9	316.4	191.3
PSA15	205.7	247.6	317.4	191.7
PSA20	201.9	245.9	318.9	196.9
Notes：T_i, T_p, and T_f are initial temperature, peak temperature and final temperature of cure exotherm; and ΔH is the enthalpy of cure exotherm

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表 2 添加不同比例ST的MDPES固化树脂的热重数据

Table 2. TGA data of the cured MDPES resin adding with different ratio of Styrene

	T_onset/℃	T_d5/℃	T_max/℃	Y_350℃%
PSA-0 ST	424	504	547	100.0
PSA-10 ST	375	497	551	99.6
PSA-15 ST	377	494	551	99.6
PSA-20 ST	374	480	552	99.6
Notes：T_onset, T_d5, and T_max are the starting decomposition temperature, the temperature at 5% mass decomposition and the temperature corresponding to the maximum decomposition rate and Y_350℃ is the mass residual rate at 350°C

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表 3 QF/PSA复合材料改性前后的力学性能和介电性能

Table 3. Mechanical and Dielectric properties of QF/PSA compsites before and after modification

	Flexural Strength/MPa		ILSS/MPa		Dielectric properties
	RT	350℃	RT	350℃	ε	tan δ
Before modification	66.38 ±6.33	40.22±5.00	5.02± 1.07	3.03±0.22	3.05±0.02	0.004± 0.001
After modification	83.83 ±8.96	58.68 ±2.54	7.68 ±0.73	6.01±1.15	3.09±0.01	0.003± 0.001

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表 4 改性前后树脂浇注体薄片的洛氏硬度测试结果

Table 4. Rockwell hardness values of flake resin casts before and after modification

	HDR/ Damage to specimens’ surface					Average of HDR
Before modification	78.5/SV	69.1/SV	62.0/SV	−/SV	−/SV	69.9
After modification	94.4/IT	94.3/IT	92.9/IT	88.6/SL	68.3/SV	87.7
Notes：HDR are Rockwell hardness values; SV-Severe damage; SL-Slight damage; IT-Intact

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