聚丙烯腈热稳定化纤维在碳化过程中的结构变化研究

为研究聚丙烯腈(PAN)热稳定化纤维在连续碳化过程中的结构和力学性能变化,于300~1 300℃对PAN稳定化纤维进行热处理,然后采用傅里叶变换红外光谱(FTIR)分析仪、X射线衍射(XRD)仪、拉曼(Raman)光谱仪、元素分析仪及纤维强伸仪等表征了纤维的化学结构、微晶结构及拉伸强度。结果表明:当温度达到600℃时,纤维残余氰基消失,结构致密性增大,且强度略有增加;当温度升高到1 000℃时,纤维氧含量大幅降低,纤维由梯形结构转变为碳平面结构,晶面堆叠、晶粒尺寸及石墨化程度缓慢增加,拉伸强度逐渐提高;当温度超过1 000℃后,微晶结构进一步重排与完善,晶粒尺寸及堆叠层数出现较快增长,同时纤维拉伸强度出现较大提升,体密度先降低后升高。     

光密度法研究预氧化工艺对纤维皮芯结构的影响

通过光密度法研究了预氧化过程中温度和时间对聚丙烯腈(PAN)基预氧化纤维皮芯结构形成和演变的影响,发现在恒定温度下对纤维进行预氧化时,250℃是纤维皮芯结构产生的温度分界点;且皮芯结构的产生具有明显的时间依赖性。同时,也跟踪了预氧化过程中纤维的氧含量变化。当预氧化温度提高后,纤维预氧化过程由反应控制转变为氧扩散控制。为了制备结构均匀的预氧化纤维,在控制纤维氧含量的同时,也应控制皮芯结构的形成。     

聚丙烯腈纤维的液相稳定化

通过液相稳定化法制备了聚丙烯腈稳定化纤维。采用密度分析、扫描电镜(SEM)、差示扫描量热分析(DSC)以及傅里叶变换红外光谱分析(FT-IR)等方法研究了在不同温度下液相稳定化所得纤维的性能,测试了碳化后纤维的力学性能。结果表明:随稳定化时间、温度的增加,纤维的致密性增加,纤维的密度逐渐增大;所得稳定化纤维表面光滑,结构均匀,截面无皮芯结构;随稳定化时间、温度的增加,纤维结构转变加快,环化度逐渐增大;碳化后纤维的力学性能良好,即使在未拉伸情况下其强度也可达到2.02GPa。     

热稳定化过程中聚丙烯腈-氧化石墨烯纤维的结构变化

采用原位聚合法制备了聚丙烯腈(PAN)-氧化石墨烯(GO)纳米复合物,并采用静电纺丝法制备了PAN及PAN-GO纳米复合物的电纺纤维。采用扫描电镜、傅里叶变换红外光谱、X射线衍射等研究了电纺纤维在恒温热稳定化过程中表面形貌、微晶结构、化学结构的变化,结果表明:恒温热处理后,纤维表面均较为光滑,GO的引入不仅能够加快热稳定化过程中环化反应的速度,而且能显著提高环化程度。     

聚丙烯腈纤维的稳定化研究进展

聚丙烯腈(PAN)纤维的稳定化是制备PAN碳纤维的关键步骤之一,综述了PAN纤维在不同介质中的稳定化过程研究以及国内外纤维改性后稳定化的研究,并简要介绍了时间、温度、张力等对稳定化过程的影响。     

硫酸处理聚丙烯腈预氧化纤维的研究

采用不同浓度的硫酸对聚丙烯腈(PAN)预氧化纤维进行处理。介绍了硫酸对PAN预氧化纤维的作用机理,探讨了硫酸浓度和处理时间对PAN预氧化纤维结构和质量的影响。通过扫描电镜(SEM)观察并定量评价纤维皮芯结构。借助傅里叶变换红外光谱(FTIR)和X射线衍射(XRD)手段对硫酸处理的PAN预氧化纤维的化学组成和晶体结构进行表征。结果表明:PAN预氧化纤维经过不同浓度硫酸处理后,通过SEM能够观察到预氧化纤维的皮芯结构,经98%硫酸处理2 min后出现孔洞,在10 min后芯部比例为10.9%,趋于稳定;在硫酸处理过程中,纤维中氰基发生水解,环化结构(C=C/C=N)特征吸收峰因化学环境的改变而红移;PAN微晶结构受到硫酸破坏,预氧化纤维环化结构仍然保存。     

DSC法研究聚丙烯腈纤维的环化反应动力学

通过差示扫描量热(DSC)法研究了聚丙烯腈(PAN)纤维的热性能及其在不同升温速率下的环化反应动力学。结果表明:PAN纤维在氮气气氛中只发生环化反应,DSC曲线的放热峰尖而窄。根据Kissinger法得出其活化能为66.86 kJ/mol,反应级数为1。由DSC曲线及外推法得到升温速率为0时,其放热峰峰值为256.8℃。随着稳定化时间的增加,PAN纤维的环化度增大,纤维稳定化程度提高。     

阻燃聚丙烯腈纤维的热分析

用热重分析法(TGA)和差示扫描量热法(DSC)研究了以卤素为阻燃剂的聚丙烯腈共聚和共混纤维的阻燃性能。研究结果表明:含卤素的PAN纤维属气相阻燃;阻燃效果与氯元素含量有关,当氯含量达到24％以上才有明显的阻燃效果;使用Sb_2O_3—氯化物体系的阻燃剂,因其协同效应而能大大地提高阻燃效果。     

聚丙烯腈纤维制备碳纤维的研究—X射线衍射法的应用

本文综述了利用广角X射线衍射分析研究聚丙烯腈(PAN)纤维制备碳纤维的预氧稳定化过程。X射线衍射法在表征PAN原丝纤维序态结构、玻璃化转变及PAN纤维在预氧化阶段的环化动力学方面已获得了广泛的应用。     

张力拉伸对PAN纤维热稳定化反应进程的影响

在不同拉伸条件下,对聚丙烯腈(PAN)纤维进行热处理。借助傅里叶变换红外光谱、X射线衍射等表征手段,研究了PAN纤维热稳定化过程中,拉伸张力对纤维分子链聚集态结构及化学反应的影响。结果表明:PAN纤维热处理过程中,施加张力会在一定程度上影响纤维的环化反应。当热处理温度较低(180℃)时,施加张力可抑制环化反应的发生;热处理温度较高(大于200℃)时,拉伸张力有利于环化反应的发生。热处理过程中,施加张力,对PAN纤维结晶度影响较小,晶区取向和全取向度增加,晶粒尺寸增大。这是由于拉伸与温度双重作用影响了纤维的聚集态结构,导致参与环化反应的分子数量发生变化。     

在氮气中处理聚丙烯腈纤维的不熔化工艺

聚丙烯腈纤维不熔化过程的前期(220℃)在氮气中热处理,后期(220℃)在空气中热处理,与常规全程空气中热处理进行对比,希望能够降低不熔化处理的成本。借助元素分析(EA)、热重分析仪(TGA)、环境扫描电子显微镜(ESEM)、力学性能分析等表征手段,研究了不同热处理方法对PAN不熔化纤维的氧化程度和皮芯结构影响以及碳化收率和碳纤维的力学性能。结果发现,与全程空气处理相比,经过氮气气氛处理后的不熔化纤维在后续处理过程中最终不熔化温度可以降低20℃,900℃碳化后的收率增加了3.8%,碳纤维的强度相当,初步估算节能8.7%。     

Influence of oxygen on the stabilization reaction of polyacrylonitrile fibers

Stabilized polyacrylonitrile (PAN) fibers pretreated under N₂ and air atmospheres were prepared and their thermal behaviors were compared by differential scanning calorimetry and thermogravimetry methods. The results indicated that the subsequent stabilization reaction of PAN pretreated in air was more obvious than that in N₂. In addition, the thermal stability of PAN pretreated in air is better than that in N₂. The structural analysis by Fourier transform infrared spectroscopy and solid state ¹³C nuclear magnetic resonance implied that oxygen promoted dehydrogenation and a compact conjugated structure was formed in PAN. In addition, the C?O structures were generated in air and increased gradually with temperature. The contents of oxygen in PAN fibers studied by elemental analysis corresponded with the structural evolution. Further investigation indicated that the C?O structures helped dehydration and also promoted formation of the cross‐linked structures. A mechanism for structural evolution in PAN during stabilization in air was proposed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Indicators for evaluation of progress in thermal stabilization reactions of polyacrylonitrile fibers

Using different indices calculated from Fourier Transform Infrared Spectroscopy (FTIR), X‐ray Diffraction (XRD), and Differential Scanning Calorimetry (DSC) spectra, progress in stabilization reactions of three different commercial grade polyacrylonitrile (PAN) fibers is calculated. From each analysis technique quantitative indices are computed which could assess in some particular reactions. Combination of these indices gives further information about the progress of stabilization reactions which cannot be concluded from single indices. The results show that different indices are not fully consistent with each other, depending on the analysis technique and the changes they assess. The advantages and disadvantages of each index are investigated and practical indices are identified which can be used to design the optimum stabilization process. In addition, by combination of some indices it is possible to separate the temperature ranges in which reactions occur in amorphous or crystalline regions. This approach can be used to design appropriate stretching process during stabilization. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40343.     

张力对聚丙烯腈纤维不熔化过程中氧化反应的影响

通过连续的不熔化实验,在不同温度段对聚丙烯腈纤维施加不同的张力,得到一系列不熔化纤维。借助差示扫描量热法(DSC)、元素分析(EA)、场发射扫描电镜(FESEM)等表征手段,研究张力在不熔化过程中对氧化反应的影响。结果表明,在175~218℃,随着张力的增大,纤维内氧含量减少,氧含量梯度(氧梯度)变化不大;在226~232℃,氧含量随张力增大先增多后减少,张力较大使得更多氧参与反应,纤维皮部与芯部氧含量差异增大,氧梯度较大;在238~270℃,随张力增大纤维内氧含量增多氧梯度增大。     

Mass DSC/TG and IR ascertained structure and color change of polyacrylonitrile fibers in air/nitrogen during thermal stabilization

The structure evolution was studied by mass spectrum (MS), differential scanning calorimetry (DSC) and thermogravimetry (TG), Fourier transform infrared (FTIR) spectroscopy. The results indicated that the CN and CC groups appeared gradually with the increase of the temperature in air and nitrogen. The CO groups appeared because of oxidative reaction in air. The CN, CC and CO groups were all chromophores. The effect of conjugated CN and CC on the absorption of the visible light was shifted to longer wavelengths and indicated π‐π* transition. There was a strong bathochromic effect as the number of CC bonds were increased. The effect of CO and –NH₂ on the absorption of the visible light was shifted to longer wavelengths and indicated n‐π* transition. Oxygen could facilitate chemical reactions in air. Hence, the color of PAN in air was deeper than in nitrogen at the same temperature. The structural change of PAN in air was faster and more complex than in nitrogen. PAN fibers treated in air turned black after 230°C. However, PAN fibers turned black at 350°C in nitrogen. The MS and FTIR indicated that cyclization occurred before dehydrogenation during stabilization in air and nitrogen. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Evolution of tension during the thermal stabilization of polyacrylonitrile fibers under different parameters

Complicated physical and chemical reactions can occur during the thermal stabilization of polyacrylonitrile (PAN) fibers, and they can be macroscopically reflected by the evolution of tension in the fibers. In this work, PAN fibers were oxidized under different parameters in a continuous production line. The tension in the fibers was examined in detail and found to be influenced greatly by the stretching ratio, temperature, and time, as well as the porosity of the PAN precursors. As the thermal stabilization proceeded, tension with different characteristics could result from various reaction mechanisms. At the initial stage, a higher temperature was helpful for lowering the tension, but the tension increased with an increasing stretching ratio. In a later stage, the tension was dominantly dependent on the cyclization reaction and increased with increasing temperature or time. Under the same stabilization conditions, the tension in low‐porosity fibers was higher than that in high‐porosity fibers. The microstructures, characterized by high‐resolution transmission electron microscopy, provided some direct evidence for the partially stabilized fibers that the stabilization in the crystalline phase was slower than that in the amorphous phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5500–5506, 2006     

Mechanism and kinetics of oxidation during the thermal stabilization of polyacrylonitrile fibers

The thermal behavior and structural evolution during the thermal stabilization of polyacrylonitrile (PAN) fibers in N₂ and air were investigated using differential scanning calorimetry and solid‐state ¹³C nuclear magnetic resonance. It was found that an oxidation reaction, that generated carbonyl (C?O) groups could occur at 160°C which has not been reported in the literature. It is proposed that the cyclized structures in the PAN macromolecule chains are a prerequisite for the oxidation. Further investigations indicate that with more cyclized structures in the PAN macromolecule chains, the oxidation proceeds more readily, which is consistent with the proposed mechanism. The kinetic parameters for the oxidation and cyclization reactions were estimated using the Kissinger method. The activation energies for the reactions of oxidation and cyclization for PAN fibers are about 96.4 kJ/mol and 190.0 kJ/mol, respectively, which implies that the cyclization is the rate determining step during the thermal stabilization of PAN fibers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Catalytic initiation of polyacrylonitrile stabilization

A catalytic surface treatment of polyacrylonitrile fibres by dibutyltin dimethoxide is investigated as to its capacity to facilitate the stabilization of the fibres to produce a satisfactory carbon fibre precursor. The stabilization is based on a combination of the catalytic treatment step and of the usual thermal oxidation step which follows. The effectiveness of the surface treatment is determined through comparing physical, thermal and mechanical properties of stabilized fibres with and without catalytic pre-treatment. The results show that a 1 minute catalytic treatment shortens the usual 220°C thermal oxidation process by at least 2 hours, and that the process is applicable in particular to polyacrylonitrile fibres which are ‘slow oxidizers’ in general due to their chemical composition.     

The conjugated plane formed in polyacrylonitrile during thermal stabilization

The formation process and mechanism of the pseudo‐graphite sheets of polyacrylonitrile (PAN) during thermal treatment in inert atmosphere were investigated by thermo‐gravimetry (TG) and X‐ray diffraction (XRD). According to the results, the conjugated plane originally formed during stabilization was proposed as the basic planar structure of the pseudo‐graphite sheets, and it was connected and stacked to form pseudo‐graphite microcrystal through chain scission reaction and non‐carbon atoms elimination reaction in 280–450 °C and 800–1300 °C respectively. The in situ measurements for time dependence of ultraviolet‐visible (UV‐vis) and Fourier transform infrared spectra (FTIR) were applied to study the conjugated plane of PAN during isothermal stabilization. It was found that with the higher temperature the conjugated plane forms more rapidly, and it has higher conjugated extent with the extending of heating time. The FTIR data showed that both cyclization and dehydrogenation are beneficial to the evolution of conjugated plane in the first 3 h, but only cyclization continues after 3 h at 250 °C. Further investigation indicated that stabilized PAN with large quantity and high conjugated extent of the conjugated plane would contribute to get large size of pseudo‐graphite microcrystal after carbonization, which is consistent with the former assumption. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43890.