聚丙烯腈浓溶液的凝胶化行为及其在聚丙烯腈碳纤维原丝制备中的应用
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摘要
聚丙烯腈(PAN)基碳纤维是碳纤维中用途最广泛、发展前景最好的一种。作为PAN基碳纤维的前驱体,PAN原丝的质量在很大程度上决定了PAN基碳纤维的性能。目前全世界对碳纤维的需求量逐年增加,然而我国生产的PAN基碳纤维总体上仍处于较低的水平,与世界先进水平差距很大。PAN原丝的质量无法满足生产高性能碳纤维的要求是制约碳纤维质量提高的重要因素,提高原丝的质量是提高我国碳纤维生产水平的当务之急。相关基础理论和制备工艺的研究对于提高原丝的质量和生产水平都是很重要的。本论文主要对作为PAN原丝的纺丝溶液的PAN/DMSO和PAN/DMSO/水浓溶液体系的凝胶化行为进行了系统研究,以PAN浓溶液的凝胶化行为和PAN凝胶的特点为依据提出了PAN原丝的新型纺丝方法,使用新型纺丝方法制备原丝并对其进行了结构性能表征。
利用动态流变实验研究了PAN/DMSO浓溶液在热致变凝胶化过程中的粘弹性,讨论了影响体系凝胶化行为的两个相互关联的参量—凝胶浓度与凝胶化转变温度对体系凝胶化行为的影响。通过对不同浓度样品的频率扫描,根据损耗角正切tanδ和动态模量G′、G″等数据以及描述凝胶化过程的标度定律得到了体系的临界凝胶浓度cg,发现在不同温度下体系的cg不同,温度越高,cg的值越大。通过温度扫描和不同温度下的频率扫描,根据损耗角正切tanδ和动态模量G′、G″等数据得到了体系的临界凝胶化转变温度Tg,发现浓度较高的样品具有较高的Tg和临界凝胶强度S。虽然不同温度下体系的cg不同,但是临界点处的松弛指数n却几乎保持不变,而具有不同Tg的体系也具有相似的n值。因此,在一定条件下形成的PAN凝胶具有其特有的结构,不随体系中PAN的浓度和温度的变化而变化。
利用动态流变测试研究了PAN/DMSO浓溶液在熟化过程中的凝胶化行为。体系在低于其临界凝胶化转变温度Tg的某一温度下恒温熟化一定的时间会发生凝胶化转变。在熟化过程中,熟化温度越低,体系的凝胶化速率越快,临界凝胶化转变时间tg越短。PAN凝胶体系符合标度定律,根据由标度定律得到的临界松弛指数n值与由实验结果直接得到的n值相符,且n值不随临界凝胶化转变时间tg的变化而变化。对于浓度相同的体系,由熟化过程得到的临界凝胶强度小于由降温过程得到的临界凝胶,表现为较大的n值和较小的S值,这很可能是因为两种情况下凝胶形成的条件不同。
浊点滴定三元相图和特征粘度测量的结果表明,体系中的含水量越高,体系越容易发生相分离。流变测试的结果表明水的存在对体系的凝胶化行为有明显影响。体系的临界凝胶化转变温度Tg随含水量的提高而升高,凝胶强度因子S随含水量的增加略有下降,而n值却几乎不变,这说明在一定条件下形成的PAN凝胶结构不受体系中含水量的影响。水的存在加速了体系的凝胶化过程,表现为临界凝胶化转变时间tg的减小。结合扫描电镜和原子力显微镜的结果可知,虽然水的存在使形成的凝胶结构更为致密,但会使体系在凝胶化过程中发生相分离,使凝胶变得不均匀,并且使凝胶的强度有所降低。
通过动态流变和AFM图像分析的方法对由PAN/DMSO/水三元体系形成的PAN凝胶的分形结构进行了研究。依据Winter的理论得到了两个不同含水量PAN凝胶样品的分形维数df可能的取值范围。利用Wu and Morbidelli的理论得到了两个PAN凝胶的分形维数df值,与由Winter的理论得到的结果符合得很好。根据Wu and Morbidelli的理论,PAN凝胶体内团簇内部的联结与团簇之间的联结对凝胶弹性的贡献比较接近。由AFM图像分析得到的PAN凝胶的df值与由两种标度定律得到的df值相符合。流变测量和图像分析的结果都表明,体系中的含水量对凝胶的df值几乎没有影响。
利用动态流变测试、差示扫描量热法(DSC)和广角X射线衍射(WAXD)等实验方法研究了PAN/DMSO和PAN/DMSO/水体系在温度变化条件下的热可逆凝胶化行为以及体系处于不同状态时(溶液或者不同条件下形成的凝胶)的结晶性。G′和G″在升温和降温过程中随温度的变化反映了PAN凝胶的热可逆性,但是在升温和降温过程中的体系粘弹性的变化是有区别的,G′和G″的变化轨迹不完全相同。另外,体系在先降温后升温和先升温后降温两个过程中的粘弹性变化也是不同的。通过动态应变扫描和剪切后的频率扫描结果发现PAN凝胶结构在受到破坏后可以迅速恢复,说明PAN凝胶的交联点不是由微晶构成的,而很可能是氰基之间的偶极一偶极相互作用。对内含溶剂的凝胶样品进行DSC测试的结果表明,单纯通过降温形成的PAN凝胶不会发生结晶,结晶不是其形成的原因。PAN溶液在凝胶化转变过程中可能会发生相分离。X射线衍射实验的结果与流变和热分析实验的结果一致,即仅依靠温度变化而形成的PAN凝胶是无定形的。但是,在非溶剂水的作用下形成的PAN凝胶是可以结晶的。结晶度和平均晶粒尺寸随凝胶中水含量的减少而增大。
使用基于降温和熟化过程中的热致变凝胶化机理的新型纺丝方法——未预凝胶化凝胶纺丝和预凝胶体凝胶纺丝以及干湿法纺丝制备了PAN基碳纤维原丝,利用扫描电镜(SEM),力学性能测试、广角X射线衍射(WAXD),小角X射线散射(SAXS)等手段对由这两种纺丝方法得到的PAN原丝进行了结构性能表征,并与由干湿法纺丝制得的原丝作了比较。使纺丝溶液在25℃的温度下熟化时,将熟化时间控制在112到190分钟之间可以使纺丝溶液发生凝胶化转变但仍具有流动性,保证了预凝胶体凝胶纺丝的可行性。与传统的干湿法纺丝相比,由未预凝胶化凝胶纺丝制得的初生纤维结构比较致密,孔洞较少,但是两者的皮芯结构差异并无明显区别。预凝胶体凝胶法纺丝时,预凝胶化的纺丝溶液由于在进入凝固浴之前已经形成了一定程度的交联网络结构而变得比较稳定,因此得到的初生纤维的截面形状比较圆,皮芯结构差异明显小于由干湿法纺丝得到的初生纤维,同时其可纺性也明显好于干湿法和未预凝胶化凝胶法纺丝。比较由干湿法纺丝、未预凝胶化凝胶法和预凝胶体凝胶法纺丝得到的原丝,由预凝胶体凝胶法得到的原丝内部孔洞体积最小,孔洞的分形维数最小,力学性能最好,由未预凝胶化凝胶法得到的原丝次之,但是由不同纺丝方法得到的原丝的结晶度差别很小。预凝胶体凝胶法优于未预凝胶化凝胶法,更优于干湿法,因为由其制得的原丝具有最优的结构和物理性能。而在两种预凝胶体凝胶纺原丝中,由萃取浴得到的原丝结构更加均一,性能也优于由凝固浴得到的原丝,并且在拉伸过程中更容易形成择优取向、堆砌完善的超分子结构。
Polyacrylonitrile (PAN)-based carbon fiber is the most widely used and promising carbon fiber. As the precursor of PAN-based carbon fiber, the quality of PAN precursor fiber determines the performance of PAN-based carbon fiber to a large extent. At present, the demand for carbon fiber is growing fast in the world. However, domestically fabricated PAN-based carbon fibers are generally at low quality level compared with those produced by some developed countries. The low-quality PAN precursor fibers are not qualified for producing high-performance carbon fiber, which has been restricting the improvement of PAN-based carbon fiber. Studies on relevant fundamental theories and fiber fabrication technics are important for improving the production level of PAN precursor fiber. In this dissertation, the gelation behavior of concentrated PAN/DMSO and PAN/DMSO/water solution which are usually used as PAN fiber spinning solutions has been systematically investigated. New spinning methods for PAN precursor fiber based on the gelation behavior and the characteristics of PAN gel have been applied to the formation of PAN precursor fibers and the structure and properties of the resultant fibers were characterized.
The viscoelastic behavior of concentrated PAN/DMSO solutions during thermal-induced gelation was investigated via dynamic rheological measurements. The effect of two correlated parameters-gel concentration and gelation temperature on the gelation behavior of the systems were discussed. The loss tangent tanδand the dynamic moduli G'andG" of different samples were obtained through frequency sweep, based on which the critical gel concentration cg was determined using scaling laws. It was found that the cg value increased with the increase of temperature. According to tanδ, G'andG" obtained from temperature sweep and frequency sweep at different temperatures, the critical gelation temperature Tg was determined and found to be proportional to the PAN concentration of the system. Also, the critical gel strength S increased with the increase of the concentration. Although cg changed with temperature, the value of the relaxation exponent n at the gel point hardly changed. The same phenomenon occurred at the critical gelation temperature Tg. It was thus concluded that PAN gel formed under certain conditions has unique structure, irrespective of the PAN concentration and the gelation temperature.
The gelation behavior of concentrated PAN/DMSO solution during aging process was investigated through dynamic rheological measurements. The system would gel after a certain period of aging at a constant temperature below its gelation temperature Tg. In the aging process, the gelation rate increased with decreasing aging temperature, which meant the critical gelation time decreased with decreasing aging temperature. Scaling laws could be applied to PAN systems. The critical n values obtained from the scaling laws were in good accordance with those obtained directly from experimental results, and the n value kept almost constant when the critical gelation time tg changed. For the systems with the same PAN concentration, the critical gel strength S of the gels formed in aging process was smaller than that of the gels formed in the cooling process, likely ascribed to the different gel forming conditions.
The results of cloud point titration and intrinsic viscosity measurements indicated that phase separation was more likely to occur when the water level was higher. The result of dynamic rheological measurements showed that water in the system could significantly affect the gelation behavior of the system. Tg was found to increase with increasing water content and S decreased a little when the water content grew. In addition, n was hardly affected by the water content, implying the structure of PAN gel formed under certain condition was hardly affected by the water level in the system. The presence of water could accelerated the gelation process, reflected by the decreased critical gelation time tg. The results of dynamic rheological measurements as well as atomic force microscopy (AFM) and scanning electron microscopy (SEM) showed that, though the presence of water made the gel structure more compact, it could lead to phase separation during the gelation process of the system. The gel thus became inhomogeneous and its strength reduced.
The fractal characteristics of PAN gels formed from PAN/DMSO/water systems were studied via dynamic rheology and AFM image analysis. The possible ranges of the fractal dimension df value for the PAN gels with different water levels were determined using Winter's theory. By applying Wu and Morbidelli's model to our gel systems, the df values for the two PAN gels of different water level were obtained and found to agree well with the results from Winter's theory. According to Wu and Morbidelli's theory, the contributions of intrafloc and interfloc links to the gel stiffness were comparable for PAN gels. Also the fractal analysis based on AFM image gave df values consistent with those obtained from the rheological measurements. The amount of water in PAN solution was found to have little effect on the df value and hence on the gel structure, and the conclusion has been confirmed by both rheology and image analyses.
Dynamic rheological measurements, differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were employed to investigate the thermoreversibility of PAN/DMSO and PAN/DMSO/water systems, and the crystallization of the systems in varied states. The changes of G'and G" during heating and cooling processes showed the thermoreversibility of PAN gel. However, the viscoelasticity changes of the systems in heating and cooling processes were different, reflected by the difference in the traces of G'and G". Besides, the viscoelasticity changes in the cooling-heating process and heating-cooling process were also different. It was found from the dynamic strain sweep and the frequency sweep after shear that the PAN gel structure could recover immediately after it was broken, which indicated that the dipole-dipole interaction between nitrile groups rather than PAN crystallites acted as the cross-linking points in PAN gels. The results of DSC tests for the solvent-containing PAN gels showed that PAN gels formed only by cooling could not crystallize, so crystallization was not the cause for the formation of PAN gel. Phase separation may occur when PAN solution underwent gelation. The results of WAXD agreed well with those of rheological measurements and thermal analyses, i.e., cooling alone could not make the resultant gel crystallize. However, the water-induced PAN gel could crystallize and the average crystallite size increased with reduced water content in the gel.
Two new spinning methods-not-pre-gelled gel spinning and pre-gel gel spinning which were on the basis of thermal-induced gelation mechanism in both cooling and aging processes were employed to produce PAN precursor fibers. The traditional dry-wet spinning was also used for comparison. SEM, mechanical tests, WAXD, small angle X-ray scattering were conducted to characterize the structure and properties of the resultant fibers. In the aging process, it was found that aging the spinning solution for 112 to 190 minutes could make the solution gel but not lose flowability, which guaranteed the feasibility of pre-gel gel spinning. Compared with the fibers produced by dry-wet spinning, the fibers from the not-pre-gelled gel spinning had more compact structure and fewer pores inside the fiber. The skin-core difference between the two types of fibers was, however, not pronounced. In pre-gel gel spinning, since the pre-gelled spinning solution had formed somewhat stable interconnected network structure, the as-spun fibers formed from the pre-gelled spinning solution possessed comparatively circular cross-section, and spinnability of the spinning solution was better. Of the fibers produced with the three methods, the pre-gel gel spun fiber had a smallest total volume of pores, smallest fractal dimension of pores and best mechanical properties. The not-pre-gelled gel spun fiber took the second place. However, the crystallinity of the three types of fibers was very close. The pre-gel gel spinning was the best spinning methods, as the fabricated fiber possessed the most favorable structure and best physical properties. For the pre-gel gel spinning, the fiber obtained from the extraction bath had better mechanical properties than that obtained from the coagulation bath. In addition, the fiber from the extraction bath had more easily oriented and better packed micro-structure.
利用动态流变实验研究了PAN/DMSO浓溶液在热致变凝胶化过程中的粘弹性,讨论了影响体系凝胶化行为的两个相互关联的参量—凝胶浓度与凝胶化转变温度对体系凝胶化行为的影响。通过对不同浓度样品的频率扫描,根据损耗角正切tanδ和动态模量G′、G″等数据以及描述凝胶化过程的标度定律得到了体系的临界凝胶浓度cg,发现在不同温度下体系的cg不同,温度越高,cg的值越大。通过温度扫描和不同温度下的频率扫描,根据损耗角正切tanδ和动态模量G′、G″等数据得到了体系的临界凝胶化转变温度Tg,发现浓度较高的样品具有较高的Tg和临界凝胶强度S。虽然不同温度下体系的cg不同,但是临界点处的松弛指数n却几乎保持不变,而具有不同Tg的体系也具有相似的n值。因此,在一定条件下形成的PAN凝胶具有其特有的结构,不随体系中PAN的浓度和温度的变化而变化。
利用动态流变测试研究了PAN/DMSO浓溶液在熟化过程中的凝胶化行为。体系在低于其临界凝胶化转变温度Tg的某一温度下恒温熟化一定的时间会发生凝胶化转变。在熟化过程中,熟化温度越低,体系的凝胶化速率越快,临界凝胶化转变时间tg越短。PAN凝胶体系符合标度定律,根据由标度定律得到的临界松弛指数n值与由实验结果直接得到的n值相符,且n值不随临界凝胶化转变时间tg的变化而变化。对于浓度相同的体系,由熟化过程得到的临界凝胶强度小于由降温过程得到的临界凝胶,表现为较大的n值和较小的S值,这很可能是因为两种情况下凝胶形成的条件不同。
浊点滴定三元相图和特征粘度测量的结果表明,体系中的含水量越高,体系越容易发生相分离。流变测试的结果表明水的存在对体系的凝胶化行为有明显影响。体系的临界凝胶化转变温度Tg随含水量的提高而升高,凝胶强度因子S随含水量的增加略有下降,而n值却几乎不变,这说明在一定条件下形成的PAN凝胶结构不受体系中含水量的影响。水的存在加速了体系的凝胶化过程,表现为临界凝胶化转变时间tg的减小。结合扫描电镜和原子力显微镜的结果可知,虽然水的存在使形成的凝胶结构更为致密,但会使体系在凝胶化过程中发生相分离,使凝胶变得不均匀,并且使凝胶的强度有所降低。
通过动态流变和AFM图像分析的方法对由PAN/DMSO/水三元体系形成的PAN凝胶的分形结构进行了研究。依据Winter的理论得到了两个不同含水量PAN凝胶样品的分形维数df可能的取值范围。利用Wu and Morbidelli的理论得到了两个PAN凝胶的分形维数df值,与由Winter的理论得到的结果符合得很好。根据Wu and Morbidelli的理论,PAN凝胶体内团簇内部的联结与团簇之间的联结对凝胶弹性的贡献比较接近。由AFM图像分析得到的PAN凝胶的df值与由两种标度定律得到的df值相符合。流变测量和图像分析的结果都表明,体系中的含水量对凝胶的df值几乎没有影响。
利用动态流变测试、差示扫描量热法(DSC)和广角X射线衍射(WAXD)等实验方法研究了PAN/DMSO和PAN/DMSO/水体系在温度变化条件下的热可逆凝胶化行为以及体系处于不同状态时(溶液或者不同条件下形成的凝胶)的结晶性。G′和G″在升温和降温过程中随温度的变化反映了PAN凝胶的热可逆性,但是在升温和降温过程中的体系粘弹性的变化是有区别的,G′和G″的变化轨迹不完全相同。另外,体系在先降温后升温和先升温后降温两个过程中的粘弹性变化也是不同的。通过动态应变扫描和剪切后的频率扫描结果发现PAN凝胶结构在受到破坏后可以迅速恢复,说明PAN凝胶的交联点不是由微晶构成的,而很可能是氰基之间的偶极一偶极相互作用。对内含溶剂的凝胶样品进行DSC测试的结果表明,单纯通过降温形成的PAN凝胶不会发生结晶,结晶不是其形成的原因。PAN溶液在凝胶化转变过程中可能会发生相分离。X射线衍射实验的结果与流变和热分析实验的结果一致,即仅依靠温度变化而形成的PAN凝胶是无定形的。但是,在非溶剂水的作用下形成的PAN凝胶是可以结晶的。结晶度和平均晶粒尺寸随凝胶中水含量的减少而增大。
使用基于降温和熟化过程中的热致变凝胶化机理的新型纺丝方法——未预凝胶化凝胶纺丝和预凝胶体凝胶纺丝以及干湿法纺丝制备了PAN基碳纤维原丝,利用扫描电镜(SEM),力学性能测试、广角X射线衍射(WAXD),小角X射线散射(SAXS)等手段对由这两种纺丝方法得到的PAN原丝进行了结构性能表征,并与由干湿法纺丝制得的原丝作了比较。使纺丝溶液在25℃的温度下熟化时,将熟化时间控制在112到190分钟之间可以使纺丝溶液发生凝胶化转变但仍具有流动性,保证了预凝胶体凝胶纺丝的可行性。与传统的干湿法纺丝相比,由未预凝胶化凝胶纺丝制得的初生纤维结构比较致密,孔洞较少,但是两者的皮芯结构差异并无明显区别。预凝胶体凝胶法纺丝时,预凝胶化的纺丝溶液由于在进入凝固浴之前已经形成了一定程度的交联网络结构而变得比较稳定,因此得到的初生纤维的截面形状比较圆,皮芯结构差异明显小于由干湿法纺丝得到的初生纤维,同时其可纺性也明显好于干湿法和未预凝胶化凝胶法纺丝。比较由干湿法纺丝、未预凝胶化凝胶法和预凝胶体凝胶法纺丝得到的原丝,由预凝胶体凝胶法得到的原丝内部孔洞体积最小,孔洞的分形维数最小,力学性能最好,由未预凝胶化凝胶法得到的原丝次之,但是由不同纺丝方法得到的原丝的结晶度差别很小。预凝胶体凝胶法优于未预凝胶化凝胶法,更优于干湿法,因为由其制得的原丝具有最优的结构和物理性能。而在两种预凝胶体凝胶纺原丝中,由萃取浴得到的原丝结构更加均一,性能也优于由凝固浴得到的原丝,并且在拉伸过程中更容易形成择优取向、堆砌完善的超分子结构。
Polyacrylonitrile (PAN)-based carbon fiber is the most widely used and promising carbon fiber. As the precursor of PAN-based carbon fiber, the quality of PAN precursor fiber determines the performance of PAN-based carbon fiber to a large extent. At present, the demand for carbon fiber is growing fast in the world. However, domestically fabricated PAN-based carbon fibers are generally at low quality level compared with those produced by some developed countries. The low-quality PAN precursor fibers are not qualified for producing high-performance carbon fiber, which has been restricting the improvement of PAN-based carbon fiber. Studies on relevant fundamental theories and fiber fabrication technics are important for improving the production level of PAN precursor fiber. In this dissertation, the gelation behavior of concentrated PAN/DMSO and PAN/DMSO/water solution which are usually used as PAN fiber spinning solutions has been systematically investigated. New spinning methods for PAN precursor fiber based on the gelation behavior and the characteristics of PAN gel have been applied to the formation of PAN precursor fibers and the structure and properties of the resultant fibers were characterized.
The viscoelastic behavior of concentrated PAN/DMSO solutions during thermal-induced gelation was investigated via dynamic rheological measurements. The effect of two correlated parameters-gel concentration and gelation temperature on the gelation behavior of the systems were discussed. The loss tangent tanδand the dynamic moduli G'andG" of different samples were obtained through frequency sweep, based on which the critical gel concentration cg was determined using scaling laws. It was found that the cg value increased with the increase of temperature. According to tanδ, G'andG" obtained from temperature sweep and frequency sweep at different temperatures, the critical gelation temperature Tg was determined and found to be proportional to the PAN concentration of the system. Also, the critical gel strength S increased with the increase of the concentration. Although cg changed with temperature, the value of the relaxation exponent n at the gel point hardly changed. The same phenomenon occurred at the critical gelation temperature Tg. It was thus concluded that PAN gel formed under certain conditions has unique structure, irrespective of the PAN concentration and the gelation temperature.
The gelation behavior of concentrated PAN/DMSO solution during aging process was investigated through dynamic rheological measurements. The system would gel after a certain period of aging at a constant temperature below its gelation temperature Tg. In the aging process, the gelation rate increased with decreasing aging temperature, which meant the critical gelation time decreased with decreasing aging temperature. Scaling laws could be applied to PAN systems. The critical n values obtained from the scaling laws were in good accordance with those obtained directly from experimental results, and the n value kept almost constant when the critical gelation time tg changed. For the systems with the same PAN concentration, the critical gel strength S of the gels formed in aging process was smaller than that of the gels formed in the cooling process, likely ascribed to the different gel forming conditions.
The results of cloud point titration and intrinsic viscosity measurements indicated that phase separation was more likely to occur when the water level was higher. The result of dynamic rheological measurements showed that water in the system could significantly affect the gelation behavior of the system. Tg was found to increase with increasing water content and S decreased a little when the water content grew. In addition, n was hardly affected by the water content, implying the structure of PAN gel formed under certain condition was hardly affected by the water level in the system. The presence of water could accelerated the gelation process, reflected by the decreased critical gelation time tg. The results of dynamic rheological measurements as well as atomic force microscopy (AFM) and scanning electron microscopy (SEM) showed that, though the presence of water made the gel structure more compact, it could lead to phase separation during the gelation process of the system. The gel thus became inhomogeneous and its strength reduced.
The fractal characteristics of PAN gels formed from PAN/DMSO/water systems were studied via dynamic rheology and AFM image analysis. The possible ranges of the fractal dimension df value for the PAN gels with different water levels were determined using Winter's theory. By applying Wu and Morbidelli's model to our gel systems, the df values for the two PAN gels of different water level were obtained and found to agree well with the results from Winter's theory. According to Wu and Morbidelli's theory, the contributions of intrafloc and interfloc links to the gel stiffness were comparable for PAN gels. Also the fractal analysis based on AFM image gave df values consistent with those obtained from the rheological measurements. The amount of water in PAN solution was found to have little effect on the df value and hence on the gel structure, and the conclusion has been confirmed by both rheology and image analyses.
Dynamic rheological measurements, differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were employed to investigate the thermoreversibility of PAN/DMSO and PAN/DMSO/water systems, and the crystallization of the systems in varied states. The changes of G'and G" during heating and cooling processes showed the thermoreversibility of PAN gel. However, the viscoelasticity changes of the systems in heating and cooling processes were different, reflected by the difference in the traces of G'and G". Besides, the viscoelasticity changes in the cooling-heating process and heating-cooling process were also different. It was found from the dynamic strain sweep and the frequency sweep after shear that the PAN gel structure could recover immediately after it was broken, which indicated that the dipole-dipole interaction between nitrile groups rather than PAN crystallites acted as the cross-linking points in PAN gels. The results of DSC tests for the solvent-containing PAN gels showed that PAN gels formed only by cooling could not crystallize, so crystallization was not the cause for the formation of PAN gel. Phase separation may occur when PAN solution underwent gelation. The results of WAXD agreed well with those of rheological measurements and thermal analyses, i.e., cooling alone could not make the resultant gel crystallize. However, the water-induced PAN gel could crystallize and the average crystallite size increased with reduced water content in the gel.
Two new spinning methods-not-pre-gelled gel spinning and pre-gel gel spinning which were on the basis of thermal-induced gelation mechanism in both cooling and aging processes were employed to produce PAN precursor fibers. The traditional dry-wet spinning was also used for comparison. SEM, mechanical tests, WAXD, small angle X-ray scattering were conducted to characterize the structure and properties of the resultant fibers. In the aging process, it was found that aging the spinning solution for 112 to 190 minutes could make the solution gel but not lose flowability, which guaranteed the feasibility of pre-gel gel spinning. Compared with the fibers produced by dry-wet spinning, the fibers from the not-pre-gelled gel spinning had more compact structure and fewer pores inside the fiber. The skin-core difference between the two types of fibers was, however, not pronounced. In pre-gel gel spinning, since the pre-gelled spinning solution had formed somewhat stable interconnected network structure, the as-spun fibers formed from the pre-gelled spinning solution possessed comparatively circular cross-section, and spinnability of the spinning solution was better. Of the fibers produced with the three methods, the pre-gel gel spun fiber had a smallest total volume of pores, smallest fractal dimension of pores and best mechanical properties. The not-pre-gelled gel spun fiber took the second place. However, the crystallinity of the three types of fibers was very close. The pre-gel gel spinning was the best spinning methods, as the fabricated fiber possessed the most favorable structure and best physical properties. For the pre-gel gel spinning, the fiber obtained from the extraction bath had better mechanical properties than that obtained from the coagulation bath. In addition, the fiber from the extraction bath had more easily oriented and better packed micro-structure.
引文
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