In-situ polysilazane modified carbon fiber for high temperature anti-oxidation
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摘要: 由于碳纤维在高温含氧的环境下易被氧化,且与基体发生强界面反应而导致其性能劣化,影响了其在复合材料领域的应用。本文通过在碳纤维表面构筑聚丙烯腈(PAN)过渡层及有机聚硅氮烷(OPSZ)陶瓷前驱体层,经低温固化与高温裂解后形成C-Si3N4保护涂层,制备了具有高温抗氧化效能的PAN-OPSZ/碳纤维。扫描电镜与能谱仪的结果表明:PAN层的涂覆有助于Si元素在碳纤维表面附着,将PAN溶液的浓度从1%提高到3%,Si元素的相对含量随即从2.81%提高到了8.26%。采用PAN与OPSZ浓度为3wt%制备的PAN-OPSZ/碳纤维的拉伸强度仅比未涂层碳纤维降低了2.08%,表明其未对碳纤维力学性能造成明显降低。制备的PAN-OPSZ/碳纤维的抗氧化能力得到了显著提高,在700℃的空气气氛下失重率低于8wt%,而未涂层碳纤维的失重率高达70wt%。以上结果说明,PAN-OPSZ涂层能有效提高碳纤维的高温抗氧化性,在碳纤维增强复合材料领域具有十分广阔的应用前景。Abstract: Carbon fiber is easily oxidized in a high-temperature oxygen-containing environment. The strong interfacial reactions with the matrix result in deterioration of their performance, which limits their use in carbon fiber-reinforced composites. In this paper, a C-Si3N4 protective coating which has high-temperature anti-oxidation performance was formed by constructing a polyacrylonitrile (PAN) layer and an organopolysilazane (OPSZ) layer on the surface of carbon fibers with curing at low-temperature and cracking at high-temperature. The results of scanning electron microscope and energy dispersive spectrometer show that the coating of PAN layer is helpful for Si element to adhere to the surface of carbon fiber. Increasing the concentration of the PAN solution from 1% to 3%, the relative content of the Si element increased from 2.81% to 8.26%. The tensile strength of PAN-OPSZ/carbon fiber prepared with PAN and OPSZ concentration of 3wt% was only 2.08% lower than that of uncoated carbon fiber, indicating that it did not cause obvious damage to the mechanical properties of carbon fiber. The oxidation resistance of the as-prepared PAN-OPSZ/carbon fibers was significantly improved, with a mass loss of less than 8wt% in an air atmosphere at 700℃, while the mass loss of uncoated carbon fibers was as high as 70wt%. The above results show that the PAN-OPSZ coating can effectively improve the high temperature oxidation resistance of carbon fibers, and has a very broad application prospect in the field of reinforced composites.
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表 1 样品名释义
Table 1. Interpretation of samples
Sample Coating Heat treatment Raw CF — — 1200℃-CF — 1200℃ for 2 h 1450℃-CF — 1450℃ for 2 h 1600℃-CF — 1600℃ for 2 h Uncoated CF — 400℃ for 0.5 h 0%PAN-9%OPSZ/CF 9%OPSZ — 2%PAN-9%OPSZ/CF 2%PAN and 9%OPSZ — 0%PAN-3%OPSZ/CF 3%OPSZ — 1%PAN-3%OPSZ/CF 1%PAN and 3%OPSZ — 2%PAN-3%OPSZ/CF 2%PAN and 3%OPSZ — 3%PAN-3%OPSZ/CF 3%PAN and 3%OPSZ — 3%PAN-5%OPSZ/CF 3%PAN and 5%OPSZ — 3%PAN-7%OPSZ/CF 3%PAN and 7%OPSZ — 3%PAN-9%OPSZ/CF 3%PAN and 9%OPSZ — 1200℃-uncoated CF — 1200℃ for 2 h 1450℃-uncoated CF — 1450℃ for 2 h 1200℃-coated CF 3%PAN and 9%OPSZ 1200℃ for 2 h 1450℃-coated CF 3%PAN and 9%OPSZ 1450℃ for 2 h 1600℃-coated CF 3%PAN and 9%OPSZ, 1600℃ for 2 h 表 2 涂层碳纤维的EDS面分析
Table 2. EDS analysis data of coated CF
Sample Coating T/℃ Element Element/wt% Atom/at% 1 1%PAN-3%OPSZ/CF 1200 C 85.36 88.97 Si 2.81 1.25 O 7.15 5.59 N 4.69 4.19 2 3%PAN-3%OPSZ/CF 1200 C 74.75 81.74 Si 8.26 3.86 O 13.16 10.80 N 3.83 3.59 3 1%PAN-9%OPSZ/CF 1200 C 82.49 86.92 Si 3.87 1.75 O 8.76 6.93 N 4.87 4.40 4 1%PAN-3%OPSZ/CF 1450 C 80.30 86.74 Si 7.04 3.26 O 6.93 4.53 N 5.73 5.47 5 3%PAN-3%OPSZ/CF 1450 C 70.11 78.29 Si 11.76 5.61 O 3.49 2.92 N 12.79 12.25 6 1%PAN-9%OPSZ/CF 1450 C 71.97 79.04 Si 7.80 3.66 O 2.83 2.33 N 14.25 13.42 Note: T—Temperature. 表 3 3%PAN涂覆组1450℃烧结后涂层纤维在700℃的热重分析数据
Table 3. Thermogravinmetric analysis data at 700℃ of 3%PAN/carbon fibers after sintering at 1450℃
Sample T1/℃ T2/℃ W1/wt% W2/wt% Uncoated CF 510 630 15.8 70.4 3%PAN-3%OPSZ/CF 700 700 0.1 7.5 3%PAN-5%OPSZ/CF 700 700 0.8 7.9 3%PAN-7%OPSZ/CF 700 700 0.9 8.2 3%PAN-9%OPSZ/CF 700 700 1.0 6.4 Notes: T1—Initial decomposition temperature; T2—Maximum decomposition temperature in the first stage; W1—Mass loss fraction at 700℃; W2—Total mass loss fraction. 表 4 1450℃烧结后的涂层碳纤维在900℃的热重分析数据
Table 4. Thermogravinmetric analysis data at 900℃ of 1450℃-coated carbon fiber
Sample T1/℃ W1/wt% W2/wt% Total weight-lessness time/min Uncoated CF 705 58.8 100.0 4.50 3%PAN-3%OPSZ/CF 735 30.8 92.6 8.00 3%PAN-5%OPSZ/CF 739 28.4 84.2 8.50 3%PAN-7%OPSZ/CF 750 22.5 87.3 14.25 3%PAN-9%OPSZ/CF 780 13.8 82.0 15.00 表 5 无涂层和有涂层CF的单丝拉伸性能
Table 5. Single silk tensile performance of uncoated and coated CF
Sample Tensile strength/
MPaStandard deviation of tensile strength/MPa Coefficient of variation (CV) for tensile strength
value/%Relative loss value of tensile strength/% 1450℃-CF 2444 293 11.98 — 1450℃-3%OPSZ/CF 2099 237 11.30 14.11 1450℃-1%PAN-3%OPSZ/CF 2179 305 13.99 10.84 1450℃-2%PAN-3%OPSZ/CF 2278 290 12.74 6.78 1450℃-3%PAN-3%OPSZ/CF 2393 246 11.23 2.08 1450℃-3%PAN-5%OPSZ/CF 2002 189 9.44 18.08 1450℃-3%PAN-7%OPSZ/CF 1496 175 11.69 38.78 1450℃-4%PAN-3%OPSZ/CF 1842 239 12.99 24.63 -
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