PAN/DMSO纺丝溶液的流变性能与挤出成型过程
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摘要
碳纤维(CF)是一种具有高强度,高模量,耐高温,耐腐蚀等一系列优异性能的新型材料。作为先进复合材料的增强纤维,其已被广泛地应用在各个领域。聚丙烯腈(PAN)纤维作为较早实现工业化的合成纤维之一,聚丙烯腈原丝能制得高性能的碳纤维,其生产工艺较其它方法简单,产品的力学性能良好,因而已成为生产碳纤维的主要原丝。聚丙烯腈原丝的结构和性能直接影响到最终的碳纤维的质量。
本文在PAN/DMSO纺丝溶液中添加高分子量PAN,并通过干湿法纺丝制备了聚丙烯腈原丝。对纺丝溶液的稳态和动态流动行为以及纤维的力学性能、结晶性能等方面进行了研究。获得了添加高分子量PAN对纺丝溶液的流变性能、可纺性和原丝性能的初步研究结果,主要开展了以下几个方面的研究工作：
采用溶液聚合的方法,在低转化率条件下,以第一单体浓度(AN)、第二单体浓度(IA)、聚合温度三个参数为考察对象,探索制备高分子量聚丙烯腈聚合物的工艺,为高分子量聚丙烯腈增强普通分子量聚丙烯腈纺丝原丝性能提供基础研究。获得最高转化率的反应条件是：AN单体浓度为45%、第二单体IA浓度为0、聚合反应温度为70℃；获得最大粘均分子量的反应条件是单体浓度为40%、第二单体IA浓度为0、聚合反应温度为50℃。
通过锥板流变仪对纺丝体系的稳态和动态流变行为进行了研究,结果表明：纺丝溶液为切力变稀流体,在较高剪切速率下,溶液出现明显的剪切变稀现象；在较低的剪切速率下,随温度的升高,溶液粘度逐渐变低。通过添加高分子量PAN,溶液粘度增大,有利于α/η适当降低,从而改善可纺性和提高纺丝稳定性；而储能模量G'略微增加,不会影响可纺性,但应控制添加量在一合适的范围。空气层高度的增加,Vim呈直线下降,要发展高喷头拉伸,应采用合适小的空气层高度。
采用干湿法纺丝制备了聚丙烯腈原丝,对纤维的形貌、结构和性能进行了详细的研究,结果表明：喷丝孔长径比(L/D)和喷头拉伸比的增大,挤出胀大效应逐渐变弱。干湿法纺丝工艺下得到的初生纤维截面均为肾形。较大的空气层高度有利于PAN大分子在拉伸力的作用下取向,但也不宜过高,空气层高度为3cm时为最优条件。喷丝孔长径比增大,纤维的断裂强度有明显的增大。总拉伸倍数高于10倍时,拉伸倍率提高,纤维强度下降,而在5-8倍之间,伸倍数提高强度有较大的提高。拉伸体系在8-10倍之间存在一最适宜拉伸倍数。喷丝孔长径比增加,原丝结晶度略微增加。二次沸水拉伸倍数增大,纤维的结晶度及晶粒在纤维轴向方向的尺寸有了较大的提高。
Carbon fiber is a kind of new-style material with a series of excellent performances, such as high tenacity, high modulus, heat-resistance, corrosion resistance and so on. As a kind of reinforcing fiber of advanced material, it is widely used in all fields. Polyacrylonitrile(PAN) fiber is one of the industrial synthetic fibers. Among the precurors available for producing carbon fibers, PAN fiber is the most commonly used and promising precursors. Now, it is popularly accepted that the quality of high-performance carbon fibers depends mainly on the structure and quality of the precursor fibers.
In this thesis, high molecular weight was added into PAN/DMSO solution, and the PAN precurors were obtained by means of dry-jet wet-spinning technology. The static and dynamic rheological behaviors of PAN/DMSO solutions and the mechanical properties and crystallinity of PAN precurors have been investigated respectively by using a cone-plate rheometer. The thesis mainly deals with the properties of precurors, the rheological behavior and Spinnability of spinning solutions with the addition of high molecular weight PAN.
By polymerizing solution, the preparation of polymers of high molecular weight polyacrylonitrile process has been explored at low conversion by means of investigating the three parameters, the first monomer (AN) concentration, the second monomer (IA)concentration, polymerization temperature. It is the basis of high molecular weigh reinforcing ordinary molecular weigh of polyacrylonitrile spinning solution. To obtain the highest conversion rate, AN concentration was 45%; the IA concentrations was 0; the polymerization reaction temperature was 70℃. Maximum viscosity average molecular weight can be obtained when AN concentration was 40%, the IA concentrations was 0; the polymerization reaction temperature was 50℃.
The Static and Dynamic Rheological Behaviors of PAN/DMSO solutions have been investigated respectively by using a cone-plate rheometer. The results showed that, the spinning solutions exhibited a shear thinning non-Newtonian fluid. The spinning solutions showed shear thinning at high shear rates. The viscosities of the solutions decreased with the rising of the temperature at low shear rate. The viscosities of the solutions increased by adding high molecular weight PAN; and it appropriately reducedα/ηeffectively, thus improving the spinnability and enhanced the spinning stability. The slight increase of storage modulus G' would not affect the spinnability, but should be controlled in a suitable scope.
The PAN precurors were obtained by means of dry-jet wet-spinning technology. The fiber morphology, structure and properties were studied in detail. The results showed that, with the increase of the ratio of length to diameter (L/D) of spinneret hole and the draw down ratio, export swell effect became weaker. The cross section of spun fibers obtained through dry and wet spinning process is kidney-shaped. The greater height of air gap contributed to the orientation of PAN molecule polymer under the action of drawing, and the proper height is 3mm. With the increase of the ratio of length to diameter (L/D) of spinneret hole, the fiber breaking strength increased significantly.10 times more than the total draw ratio, the draw ratio increased and fiber strength decreased. When 5-8 times, the strength greatly improved. There exists a most appropriate tension between 8 to 10 times. While L/D increases, precursor crystallinity increases slightly. With the increase of second boiling water draw ratio, the fiber crystallinity and grain size in the fiber axial direction have been greatly improved.
本文在PAN/DMSO纺丝溶液中添加高分子量PAN,并通过干湿法纺丝制备了聚丙烯腈原丝。对纺丝溶液的稳态和动态流动行为以及纤维的力学性能、结晶性能等方面进行了研究。获得了添加高分子量PAN对纺丝溶液的流变性能、可纺性和原丝性能的初步研究结果,主要开展了以下几个方面的研究工作：
采用溶液聚合的方法,在低转化率条件下,以第一单体浓度(AN)、第二单体浓度(IA)、聚合温度三个参数为考察对象,探索制备高分子量聚丙烯腈聚合物的工艺,为高分子量聚丙烯腈增强普通分子量聚丙烯腈纺丝原丝性能提供基础研究。获得最高转化率的反应条件是：AN单体浓度为45%、第二单体IA浓度为0、聚合反应温度为70℃；获得最大粘均分子量的反应条件是单体浓度为40%、第二单体IA浓度为0、聚合反应温度为50℃。
通过锥板流变仪对纺丝体系的稳态和动态流变行为进行了研究,结果表明：纺丝溶液为切力变稀流体,在较高剪切速率下,溶液出现明显的剪切变稀现象；在较低的剪切速率下,随温度的升高,溶液粘度逐渐变低。通过添加高分子量PAN,溶液粘度增大,有利于α/η适当降低,从而改善可纺性和提高纺丝稳定性；而储能模量G'略微增加,不会影响可纺性,但应控制添加量在一合适的范围。空气层高度的增加,Vim呈直线下降,要发展高喷头拉伸,应采用合适小的空气层高度。
采用干湿法纺丝制备了聚丙烯腈原丝,对纤维的形貌、结构和性能进行了详细的研究,结果表明：喷丝孔长径比(L/D)和喷头拉伸比的增大,挤出胀大效应逐渐变弱。干湿法纺丝工艺下得到的初生纤维截面均为肾形。较大的空气层高度有利于PAN大分子在拉伸力的作用下取向,但也不宜过高,空气层高度为3cm时为最优条件。喷丝孔长径比增大,纤维的断裂强度有明显的增大。总拉伸倍数高于10倍时,拉伸倍率提高,纤维强度下降,而在5-8倍之间,伸倍数提高强度有较大的提高。拉伸体系在8-10倍之间存在一最适宜拉伸倍数。喷丝孔长径比增加,原丝结晶度略微增加。二次沸水拉伸倍数增大,纤维的结晶度及晶粒在纤维轴向方向的尺寸有了较大的提高。
Carbon fiber is a kind of new-style material with a series of excellent performances, such as high tenacity, high modulus, heat-resistance, corrosion resistance and so on. As a kind of reinforcing fiber of advanced material, it is widely used in all fields. Polyacrylonitrile(PAN) fiber is one of the industrial synthetic fibers. Among the precurors available for producing carbon fibers, PAN fiber is the most commonly used and promising precursors. Now, it is popularly accepted that the quality of high-performance carbon fibers depends mainly on the structure and quality of the precursor fibers.
In this thesis, high molecular weight was added into PAN/DMSO solution, and the PAN precurors were obtained by means of dry-jet wet-spinning technology. The static and dynamic rheological behaviors of PAN/DMSO solutions and the mechanical properties and crystallinity of PAN precurors have been investigated respectively by using a cone-plate rheometer. The thesis mainly deals with the properties of precurors, the rheological behavior and Spinnability of spinning solutions with the addition of high molecular weight PAN.
By polymerizing solution, the preparation of polymers of high molecular weight polyacrylonitrile process has been explored at low conversion by means of investigating the three parameters, the first monomer (AN) concentration, the second monomer (IA)concentration, polymerization temperature. It is the basis of high molecular weigh reinforcing ordinary molecular weigh of polyacrylonitrile spinning solution. To obtain the highest conversion rate, AN concentration was 45%; the IA concentrations was 0; the polymerization reaction temperature was 70℃. Maximum viscosity average molecular weight can be obtained when AN concentration was 40%, the IA concentrations was 0; the polymerization reaction temperature was 50℃.
The Static and Dynamic Rheological Behaviors of PAN/DMSO solutions have been investigated respectively by using a cone-plate rheometer. The results showed that, the spinning solutions exhibited a shear thinning non-Newtonian fluid. The spinning solutions showed shear thinning at high shear rates. The viscosities of the solutions decreased with the rising of the temperature at low shear rate. The viscosities of the solutions increased by adding high molecular weight PAN; and it appropriately reducedα/ηeffectively, thus improving the spinnability and enhanced the spinning stability. The slight increase of storage modulus G' would not affect the spinnability, but should be controlled in a suitable scope.
The PAN precurors were obtained by means of dry-jet wet-spinning technology. The fiber morphology, structure and properties were studied in detail. The results showed that, with the increase of the ratio of length to diameter (L/D) of spinneret hole and the draw down ratio, export swell effect became weaker. The cross section of spun fibers obtained through dry and wet spinning process is kidney-shaped. The greater height of air gap contributed to the orientation of PAN molecule polymer under the action of drawing, and the proper height is 3mm. With the increase of the ratio of length to diameter (L/D) of spinneret hole, the fiber breaking strength increased significantly.10 times more than the total draw ratio, the draw ratio increased and fiber strength decreased. When 5-8 times, the strength greatly improved. There exists a most appropriate tension between 8 to 10 times. While L/D increases, precursor crystallinity increases slightly. With the increase of second boiling water draw ratio, the fiber crystallinity and grain size in the fiber axial direction have been greatly improved.
引文
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