摘要
聚丙烯腈(PAN)纤维的取向结构是影响纤维力学性能的关键因素。在碳纤维制备过程中，PAN原丝高分子链取向结构经历热稳定化过程，发生复杂的物理和化学变化，影响进一步碳化过程生成的石墨微晶结构，从而对终极碳纤维性能产生影响。本论文针对PAN原丝取向结构在热稳定化过程中的演变规律及取向结构对热稳定化反应程度及反应生成结构的影响进行了研究分析，揭示了取向结构影响热稳定化反应的机理及影响特点；并通过外力场牵伸改变取向结构，研究该过程对热稳定化反应及生成碳纤维结构和性能的影响，揭示了牵伸诱导取向对热稳定化特征结构及碳纤维性能的影响关系，为高性能碳纤维的结构可控性制备提供了机理依据。
PAN纤维取向结构在热稳定化过程中的演变规律主要受到分子链侧氰基环化反应的影响。发生在非晶区的环化反应促进体系内应力增加，能够诱导晶区分子链进一步取向重排，导致晶区取向度增大；相应的，环化应力还能诱导近晶区分子链段规整重排形成晶区，导致结晶度和晶粒尺寸小幅增大。时温效应对环化反应影响显著，导致不同时间温度环化应力诱导PAN纤维聚集态结构变化存在差异：热处理180℃时，环化反应程度较低，环化应力诱导结晶和晶区取向现象不明显；200℃热处理30min后，随着环化反应程度提高，环化应力诱导结晶和晶区取向现象逐渐显现；220℃热处理初期，剧烈的环化反应使得应力诱导结晶和晶区取向现象更加明显，影响PAN纤维结晶度、晶粒尺寸和晶区取向度短时间内迅速增长，但随着热处理时间延长，晶区分子链逐渐参与环化反应，原有晶态规整结构被破坏，导致220℃热处理30min后，晶态结构参数逐渐减小；240℃热处理时，纤维非晶区和晶区分子链短时间内迅速参与环化反应，结晶度、晶粒尺寸和晶区取向度均显著降低。
空气气氛热稳定化反应中，由于环境介质氧对环化反应有催化作用，显著缩短了环化反应诱导期，导致PAN纤维晶态结构和取向结构演变特征温度向低温方向推移。
PAN纤维取向结构影响热稳定化反应放热行为，热稳定化反应初期，纤维取向结构对反应有抑制作用，取向度较大的纤维，初始热稳定化反应放热量相对较低；随热处理温度升高，取向分子链逐渐参与化学反应，取向结构对反应的抑制作用不断减弱；热稳定化反应中后期，取向结构越规整的纤维，热稳定化反应放热相对更加剧烈。
PAN纤维取向结构影响热稳定化结构的形成，取向度较高的纤维，容易生成较多热稳定化类芳香片层结构，且片层面积相对较大。对热稳定化PAN纤维应力-应变曲线的研究表明，类芳香片层结构生长越完善的纤维，其断裂伸长率相对更大，由于取向度较高的纤维生成类芳香结构相对更完善，因此影响其热稳定化纤维的拉伸强度、拉伸模量和断裂伸长率相对更大。
热稳定化同步牵伸影响PAN纤维取向结构，进而影响热稳定化反应。与原丝牵伸相比，200℃以下热稳定化牵伸能够进一步提高纤维晶区取向度：随热处理温度升高，牵伸率增大，晶区取向度不断增大；但较高温度时取向度随牵伸率变化增长逐渐缓慢。受牵伸对取向结构的影响，牵伸诱导取向度增长较大的纤维，其热稳定化纤维中环化反应程度相对更高，生成的类芳香片层结构相对更多。200℃热处理8min后追加牵伸，对晶区取向结构及热稳定化反应的影响已不明显。
不同热稳定化牵伸制备的PAN基碳纤维石墨结构和力学性能的研究表明，热稳定化牵伸诱导取向度增长较大的纤维，由于促进了热稳定化过程生成更大类芳香片层结构，因此影响制得碳纤维的石墨化程度相对更好，石墨结构相对更均一，碳纤维的拉伸强度和拉伸模量相对更大。
The axial mechanical properties of polyacrylonitrile (PAN) basedcarbon fiber was originated from its orientation structure. During thestabilization process, which was one of the key process for the manufactureof high performance carbon fiber from the PAN precursor, complicatedphysical and chemical transition of the oriented PAN molecular chains wereoccurred and it was very important for the formation of pseudo-graphitecrystalline structure and properties of the resulted carbon fiber. In presentstudy,the effect of orientation structure of PANprecursor on the stabilizationprocess, including the structure transformation and the extent of cyclizationwas investigated. The characteristic correlation between the orientationstructure and the mechanism of stabilization process was revealed.Stretching was performed during the stabilization process and the effect ofwhich on the structure as well as properties of final carbon fiber was alsostudied. The author believes this study can contribute to the development of the research field of high performance carbon fiber.
During the thermal stabilization process, from the viewpoint ofmicroscopic, the evolution of the orientation structure was related to thecyclization of the nitrile side group. The orientation degree of crystalline partwas increased because of the rearrangement of molecular chains under thestress, which was caused by the cyclization started from the amorphous part.At the same time, the molecular chains in the pseudo-crystalline region couldbe regularly arranged and lead to the increase of crystallinity and crystallitesize. As for the environment factors, the evolution of aggregation structurewas influenced by the time and temperature as well since the cyclizationprocess was different.When the heat treatment temperature was180oC， thecyclization degree was low so that the induced crystallization and orientationof crystalline part was not obviously.After heated at200oC for30minutes,with the increasing of the cyclization degree, the above phenomenon couldbe observed gradually.In the case of being heated at220oC，at the beginning,the crystallinity, crystallite size and orientation degree of crystalline partwere increased rapidly because of the induced crystallization andrearrangement of molecular chains. However, with the extension of heatingtime, the crystalline molecular chains started to participate the cyclizationand lead to the destruction of the whole crystalline structure, the crystallinity,crystallite size and orientation degree were decreased. When the heatingtemperature reached to240oC, the cyclization occurred in both amorphous and crystalline region rapidly, the crystalline structure factors abovedecreased obviously.
When the stabilization process was performed in air, since thecyclization could be initialized by oxygen, the induction period of thecyclization was reduced so that the transition of aggregation structure wouldoccur at relative lower temperature.
The effect of orientation structure of PAN precursor on the exothermalof stabilization reaction was investigated on the basis of differential scancalorimeter measurements. Initially, the cyclization was constrained and theexothermic heat flow was relatively lower if the orientation of PANfiber ishigher. With the increasing of temperature, the confinement of theorientation structure was decreased since the oriented chain participate thecyclization gradually. In the middle and last stage of stabilization, theendothermic peak was sharper for the PAN fiber with higher orientationdegree.
The formation of cyclizated structure was also related to the orientationstructure. The measurements of13C-NMR indicate that relatively more andlarger aromatic layer structure, which was benefit to the mechanicalproperties of carbon fiber such as elongation, tensile strength, tensilemodules, was easy to obtain from the PAN precursor with higher orientation.
As mentioned above, the cylization reaction was related to theorientation structure of PANfiber, and it was also affected by the stretching during stabilization. Comparing to the stretching during precursor processingstage, the stretching during stabilization below200oC is more useful toincrease the orientation degree of crystalline part. With the increase ofheating temperature, the orientation degree of crystalline part was increasedwith stretching ratio, while the tendency was slow down. The cyclizationdegree and aromatic layer structure was relatively larger for the PANfiberwith higher orientation degree. On the other hand, stretching after heattreatment at200oC for8min has almost no effect on the orientation structureof crystalline part.
The pseudo-graphite structure and mechanical properties of so obtainedcarbon fiber were measured. It is easy to obtain larger and more regulararomatic layer structure by performing higher stretching during thermalstabilization while the pseudo-graphite structure is more homogeneous andgraphite degree is higher, which is very useful to improve the mechanicalproperties of final carbon fiber.
引文
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