Preparation and properties of novel silicon-containing polyarylacetylene resin based wave-transparent composite
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摘要: 为满足工程领域对耐高温树脂基透波复合材料的需求，研究石英纤维(QF)增强新型含硅改性聚芳炔(PSA)树脂基复合材料(QF/PSA)的制备方法及其性能。首先对树脂的黏度进行分析，确定了树脂在不同温度和时间下的黏度变化预测模型，适宜的树脂传递模塑工艺(Resin Transfer Molding, RTM)注胶温度在70~100℃范围；对树脂固化过程中的放热量、红外光谱和流变特性进行分析，确定了树脂的固化温度和固化过程，在250℃可以实现树脂的固化。基于上述分析进行了复合材料的高质量制备，并进一步对复合材料的微观形貌、力学性能、热膨胀性能、介电性能和耐高温性能进行分析和试验验证。材料的玻璃化转变温度(Tg)大于500℃，5%热失重温度(T5%)高达625℃，石英灯试验表明耐高温能力可达520℃/1000 s；介电常数稳定在3.1~3.2，介电损耗稳定在0.003以下；力学性能满足功能材料的使用要求。上述研究表明，该新型含硅聚芳炔树脂基透波复合材料在航空航天领域具有重要的应用价值。Abstract: In order to satisfy the requirement of high-temperature resistant wave-transparent composite in project field, a quartz fiber (QF) reinforced novel silicon-containing polyarylacetylene (PSA) resin based composite (QF/PSA) was researched and characterized. Firstly, viscosity prediction model of different temperature and time was established based on the viscosity-time curves of the resin, the model indicates that the resin can be injected between 70~100℃ for resin transfer molding (RTM) process. The curing heat, FT-IR spectra and rheological behavior of the resin were analysized, then the curing temperature and process were revealed. The results show that the resin can be curved at 250℃. Based on the above research, the high-quality preparation of the composite was achieved. Furthermore, the micro-morphology, mechanical properties, thermal expansion performance, dielectric properties as well as high temperature resistant performance of the composite were investigated and verified by experiments. The composite exhibits excellent thermal stability with Tg above 500℃ and T5% up to 625℃, and quartz lamp experiment further indicates that the high temperature resistant ability is up to 520℃/1000 s. The dielectric constant is 3.1~3.2 and dielectric loss is less than 0.003. In addition, the mechanical property is enough for functional composite. The above research indicates that the novel silicon-containing polyarylacetylene resin based wave-transparent composite has high potentials in the fields of aeronautics and astronautics.
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图 1 含硅聚芳炔(PSA)树脂的分子结构
Figure 1. The molecular structure of the silicon-containing polyarylacetylene (PSA) resin
图 2 不同温度下PSA树脂的黏度-时间曲线
Figure 2. Viscosity-time curves of the PSA resin at different temperature
图 3 PSA树脂的
$\rm ln\left( {{\rm \eta / {{\rm \eta _0}}}} \right)$ -$t$ 曲线图Figure 3.
$\rm ln\left( {{\eta / {{\eta _0}}}} \right)$ -$t$ curves of the PSA resin
图 4 PSA树脂的黏度模型曲线与测试数据的对比
Figure 4. Comparison of viscosity prediction curves and test values of PSA resin
图 7 PSA树脂不同升温速率下的固化温度及拟合曲线
Figure 7. Curing temperature and the fitting curves of PSA resin at different heating rate
图 11 石英纤维 (QF)/PSA复合材料内部的光学显微镜和SEM图像
Figure 11. Optical microscope and SEM images of quartz fiber (QF)/PSA composite
图 12 不同温度下QF/PSA复合材料的弯曲强度、弯曲模量和层间剪切强度
Figure 12. Flexural strength, flexural modulus, and interlaminate shear strength of the QF/PSA composite at different temperature
图 13 QF/PSA复合材料面内和垂直于面内的热机械曲线
Figure 13. TMA curves of the QF/PSA composite parallel and perpendicular to layers
图 16 PSA和PAA树脂浇注体在空气和氮气氛围中的热失重曲线(升温速率：5℃/min)
Figure 16. TGA traces of PSA and PAA casting bodies in air and nitrogen (heating rate: 5℃/min)
图 17 QF/PSA复合材料试验件高温试验前后的照片
Figure 17. Images of the QF/PSA composite before and after high temperature test
图 18 QF/PSA复合材料高温试验之后超声和CT图像
Figure 18. Ultrasonic detecting and CT images of the QF/PSA composite after high temperature test
表 1 PSA树脂不同温度下的模型参数
$n$ 值Table 1. Fitting values of viscosity model parameter
$n$ of PSATemperature/℃ Model parameter $n$ 80 0.0201 90 0.0318 100 0.0646 110 0.0998 
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表 2 PSA树脂不同温度下的RTM注胶工艺窗口
Table 2. The PSA resin RTM injection processing window of different temperature
Temperature/℃ RTM injection time/h 60 0 70 0-17.8 80 0-31.8 90 0-29.5 100 0.5-23.4 110 3.9-17.5 120 4.5-12.7 130 4.1-9.1
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表 3 QF/PSA复合材料与QF/聚芳炔(PAA)复合材料的室温力学性能
Table 3. Mechanical properties of the QF/PSA composite and QF/aromatic alkyne (PAA) composite at room temperature
Composite Tensile strength/MPa Tensile modulus/GPa Compressive strength/MPa Compressive modulus/GPa Flexural strength/MPa Flexural Modulus/GPa Interlaminate shear strength/MPa QF/PSA 388 23.4 152 28.4 252 25.5 17.7 QF/PAA 161 16.0 92 14.4 172 16.5 14.5
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