PAN基大丝束碳纤维原丝热氧稳定化过程聚热行为解析

Heat accumulation behavior during thermo-oxidative stabilization of large-tow PAN-based carbon fiber precursors

  • 摘要: 为明确PAN基大丝束碳纤维原丝热氧稳定化过程中的束内聚热来源,本文采用原位中心局部温度监测、皮芯结构观察、傅里叶变换红外光谱(FT-IR)和差示扫描量热法(DSC)等方法,研究丝束规格、展宽状态及反应热源位置对温度响应和径向结构均匀性的影响;同时构建PAN原丝/完全稳定化纤维复合丝束,在近似丝束形貌和几何传热路径条件下,对环境传热、外层反应热传导和内部反应热的表观贡献进行定性—半定量分析。结果表明,12 K和24 K丝束在242℃下反应较平稳,48 K和72 K丝束出现明显热聚集,96 K丝束在致密堆积状态下易发生热失控;将96 K丝束由5 mm展宽至30 mm后,中心局部峰值温度明显降低。结构表征显示,48 K和96 K丝束均出现皮芯结构,且96 K中心纤维最为明显;FT-IR结果表明,稳定化前期表层纤维反应程度较高,随后中心局部区域因反应热积累而加速反应,96 K丝束约在6 min时中心纤维反应程度反超表层纤维。复合丝束实验显示,内部PAN纤维反应放热与96 K丝束中心局部峰值温度近似呈线性关系,每增加24 K内部PAN纤维,中心局部峰值温度约提高2.9℃;采用稳定化前1 min内中心局部平均升温速率表征初期环境传热效率,结果表明每增加24 K纤维,该平均升温速率约降低8.9℃/min。外层PAN纤维释放的反应热可向中心区域传递,但其有效贡献受热源位置、外表面散热和束内传热路径共同影响,呈非线性特征。上述结果表明,内部反应热持续释放与束内散热受阻的耦合作用是大丝束PAN纤维热氧稳定化聚热的重要来源。

     

    Abstract: To clarify the origin of heat accumulation in large-tow polyacrylonitrile (PAN)-based carbon fiber precursors during thermo-oxidative stabilization, this work investigated the effects of tow size, spreading state and reaction-heat source on local center-temperature response and radial structural inhomogeneity. In-situ local center-temperature monitoring, skin-core structure observation, Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC) were used. Composite bundles composed of PAN precursors and fully stabilized fibers were further designed to evaluate, in a qualitative and semi-quantitative manner, the apparent contributions of environmental heat transfer, heat transferred from outer reacting fibers and heat released by inner reacting fibers. The results show that 12 K and 24 K bundles reacted steadily at 242℃, whereas 48 K and 72 K bundles exhibited obvious heat accumulation and densely packed 96 K bundles tended to undergo thermal runaway. Increasing the spreading width reduced the local center peak temperature of 96 K bundles, indicating an overall improvement in heat dissipation. FT-IR results show that surface fibers reacted faster at the early stage, while the central fibers accelerated later because of local heat accumulation; for 96 K bundles, the reaction degree of the central fibers exceeded that of the surface fibers at about 6 min. In the composite-bundle model, each additional 24 K inner PAN fibers increased the local center peak temperature of the 96 K composite bundle by about 2.9℃. When the average local center heating rate within the first 1 min was used to describe the initial environmental heat-transfer efficiency, each additional 24 K fibers reduced this value by about 8.9℃/min. These results indicate that heat accumulation in large-tow PAN precursor bundles mainly originates from the combined effect of continuous heat release from inner PAN fibers and hindered heat dissipation within the bundle.

     

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