高强高模碳纤维/双马复合材料的耐高温界面相设计及其热氧老化性能研究

Design of high temperature resistance interphase and study on thermo-oxidative aging properties of high strength high modulus carbon fiber/bismaleimide composites

  • 摘要: 高强高模碳纤维/双马复合材料(CF/BMI)在航天领域耐高温结构件的应用日益广泛,随着耐高温双马树脂的耐热等级不断提高,复合材料在热氧环境中长期服役的安全可靠性,高度依赖于界面相的热氧稳定性。为此,本文制备了具有不同支化度的超支化聚酰胺酸(HBPAA)上浆剂,在碳纤维表面构筑了超支化聚酰亚胺(HBPI)耐高温界面相,表征了双马树脂(BMI)和HBPI的耐热性,分析了热氧老化前后碳纤维表面的物化特性,并探究了25℃、200℃、250℃和300℃热氧老化168 h后,不同支化度HBPI耐高温界面相对碳纤维/双马复合材料的界面剪切强度和界面韧性的影响,同时结合界面相模量与结构的变化,提出了碳纤维/双马复合材料的热氧老化机制。研究结果表明:将三种不同支化度(0.42、0.61、0.81)的HBPAA经酰亚胺化处理后,得到HBPI的玻璃化转变温度随着支化度增大而逐步提升,分别达到297℃、310℃和312℃。与去浆碳纤维相比,HBPI显著提高了碳纤维表面的化学活性及热氧稳定性。相比除浆碳纤维/双马复合材料(p-CF/BMI),改性后碳纤维/双马复合材料(HBPI1-CF/BMI、HBPI2-CF/BMI和、HBPI3-CF/BMI)在热氧老化后的界面性能显著提升,在300℃热氧老化168 h后,HBPI2-CF/BMI的界面剪切强度和界面韧性最佳,其界面相厚度最大且界面模量差被有效的缓解,主要归因于支化度适中(0.61)的HBPI2兼具刚性主链和超支化拓扑结构,同步过渡界面相模量并分散界面热应力,此外HBPI2与BMI树脂的化学键合有效抑制了热氧环境中的界面脱粘,最终赋予复合材料更优异的界面性能与耐热氧老化性能。

     

    Abstract: High strength high modulus carbon fiber reinforced bismaleimide composites (CF/BMI) have been widely used in aerospace applications for structural components with high temperature resistance. With the continuous improvement in the heat resistance level of high temperature bismaleimide (BMI) resins, the safety and reliability for long-term service at high temperature environments have been highly dependent on the thermo-oxidative aging stability of the interphase of composite. Herein, HBPAA sizing agents with different degrees of branching (DB) were prepared, and used to construct hyperbranched polyimide (HBPI) interphases with high temperature resistance on carbon fibers. The heat resistance of BMI resin and HBPI were investigated, and the thermo-oxidative stability of carbon fiber surface was analysed. The effects of HBPI interphases with different DB on interfacial shear strength and interfacial toughness of CF/BMI composites were explored after thermo-oxidative aging at 25℃, 200℃, 250℃, and 300℃ for 168 h. According to the interfacial properties as well as the interfacial modulus and structure of CF/BMI composites, the thermo-oxidative aging mechanism of the composites were summarized. Results showed that after imidization treatment of HBPAA with three different DB (0.42, 0.61, 0.81), the glass transition temperature of HBPI were increased with the DB increasing reaching 297℃, 310℃ and 312℃. Compared to those of pristine carbon fibers, the chemical activity and thermo-oxidative stability of carbon fibers were improved by HBPI. Compared to p-CF/BMI, the modified composites (HBPI1-CF/BMI, HBPI2-CF/BMI and HBPI3-CF/BMI) exhibited the improved interfacial properties after thermo-oxidative aging. After thermo-oxidative aging at 300℃ for 168 h, the highest interfacial shear strength and interfacial toughness of CF/BMI (HBPI2-CF/BMI) were obtained. The thickest interphase effectively alleviated the interfacial modulus disparity in HBPI2-CF/BMI composite, which was attributed to the rigid framework and the hyperbranched topological structure of HBPI2 with moderate DB (0.61), as well as transitioning the interfacial modulus and dissipating the interfacial thermal stress. In addition, the interfacial debonding under thermo-oxidative conditions was suppressed due to chemical bonding between HBPI2 and BMI resin, ultimately endowing the better interfacial performance and resistance to thermo-oxidative aging of the composites.

     

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