饱和蒸汽牵伸工艺改进与聚丙烯腈原丝相关性研究
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摘要
聚丙烯腈纤维是制备高性能碳纤维的主要前躯体。原丝的各项性能对最终产品碳纤维有着重要的影响。聚丙烯腈原丝质量的低下是制约我国碳纤维发展的瓶颈。由于PAN原丝在纺丝过程中形成的各种缺陷,将进一步“遗传”给后续的碳纤维,从而极大的降低其性能。所以研究聚丙烯腈原丝的纺丝工艺与纤维性能的关系,掌握纺丝工艺与原丝性能的相关性,对于改善和提高原丝性能有着十分重要的意义。
初生纤维的大分子结构缺乏定向排列,纤维的强度低,要制备高性能的碳纤维原丝必须对纤维进行牵伸以提高取向度。由于一级牵伸的倍数十分有限,无法让纤维达到所需的力学性能。因此,必须采用二级或多级牵伸。通过饱和蒸汽对原丝的高倍牵伸是提高原丝性能的关键技术之一。但是,国内现有的饱和蒸汽工艺除了保温性、蒸汽密封性没有达到应有的要求外,由于拉伸方式的限制,丝束无法充分升温、润湿,就被高倍拉伸,导致大量毛丝甚至断丝的发生。
本文通过对饱和蒸汽拉伸机理的深入分析,通过牵伸装置的多项改进,设计了一个由两个密闭室组成的牵伸装置——两段合一式拉伸装置,在原有的加热拉伸部分前,增添一个密闭的预热部分,而预热部分的饱和蒸汽温度、湿度和蒸汽压力比加热部分低,使得丝束在加热拉伸前,能进行充分的润湿和加热,从而减少拉伸中产生的毛丝数。通过改进前后三个实验装置对原丝的工艺参数和工艺性的对比,证明了两段合一式拉伸方式,具有不可比拟的优越性,也极大地提高了原丝蒸汽拉伸的工艺性,毛丝与断头数大大减轻。
本文通过X射线衍射、扫描电镜、声速法以及单丝拉伸等测试手段,测试了实验原丝的强度、断裂伸长率、密度、沸水收缩率、结晶度、取向度和晶粒尺寸等参数。系统研究了饱和蒸汽牵伸对PAN原丝结构与性能的影响。结果表明,加热段蒸汽压为5 kg/cm~(2),同管两段不同牵伸域的压力差在2kg/cm~(2)时,原丝的各项力学性能都达到最佳。
由X-射线衍射得到的原丝结晶度随着拉伸倍数的增加而增加,而晶面间距没有太大的变化;由声速法和X-射线衍射法测定的取向度均随着拉伸程度的增加而提高;纤维沸水收缩率的变化研究,发现纤维的内应力与牵伸的倍数和温度有关。而适当控制牵伸过程中的张力和湿度的大小,可以提高纤维的力学性能。扫描电镜的图片的对比表明,两段合一式饱和蒸汽牵伸装置制得的原丝直径更均匀,表面平整且沟槽清晰、细致和均匀,具有更为优化的微观结构。在三种拉伸方式的对比中结果均表明:两段合一式拉伸方式的原丝具有更加优越的结构性能。为现有原丝生产工艺的改进,为高性能的碳纤维原丝的制备创造了有利的条件。
PAN fiber is the key precursor of the high-performance carbon fiber preparation,which has a significant impact on carbon fiber.The PAN precursor's low quality is the bottleneck that hinders the development of carbon fiber in China.Therefore,research on the relationship between PAN filament spinning process and the fiber properties has great significance for improving and enhancing the performance of the carbon fibers.
Because the macromolecular structure of the primary fiber is lack of directional orientation, then its strength is very low.For improving the fiber strength,we need increase its orientation by drawing.The effect of single drafting is limited which could not achieve the mechanical requirement.Therefore,we must use two or multi-level drawing.Drafting the fiber by saturated steam is one of the key technologies to improve the performance of the precursor.However,the technology of this field in our country has many defects,which resulted in the occurrence of broken fiber.
In this paper,X-ray diffraction,scanning electron microscopy,sound velocity method,and single-tow stretch were employed to test experimental precursors' strength,breaking elongation, density,boiling water shrinkage,the degree of crystallinity and orientation,and grain size,etc. Intensive research was carried out on the drafting under the saturated steam's effect on the structure and performance of the PAN.The results showed that the mechanical properties of precursor are best when the vapor pressure is 5 kg/cm~2 and the pressure difference between two different domains in the of drawing tube is 2kg/cm~2.
The crystallinity degree of the precursor was obtained from X-ray diffraction.With the increasing of draw ratio,the crystal space is not changed.The sound velocity method and X-ray diffraction measurement showed that the degree of orientation increased with the growth of tensility.The research on the change rate of fiber boiling water shrinkage indicated that fiber stress was related to the drawing of the multiple and temperature.The proper control of the drawing tension and humidity can increase the fiber mechanical properties.The comparative picture of scanning electron microscope showed that two-one-type saturated steam drawing device can obtain the precursor with uniform diameter,smooth surface and clear groove,as well as a more optimized micro-architecture.The results of the comparison with three stretching modes showed that two-one-type precursor had more superior structure performances.It improved the existing process of PAN precursor production and created proper experiment conditions for the high-performance carbon fiber precursor preparation.
初生纤维的大分子结构缺乏定向排列,纤维的强度低,要制备高性能的碳纤维原丝必须对纤维进行牵伸以提高取向度。由于一级牵伸的倍数十分有限,无法让纤维达到所需的力学性能。因此,必须采用二级或多级牵伸。通过饱和蒸汽对原丝的高倍牵伸是提高原丝性能的关键技术之一。但是,国内现有的饱和蒸汽工艺除了保温性、蒸汽密封性没有达到应有的要求外,由于拉伸方式的限制,丝束无法充分升温、润湿,就被高倍拉伸,导致大量毛丝甚至断丝的发生。
本文通过对饱和蒸汽拉伸机理的深入分析,通过牵伸装置的多项改进,设计了一个由两个密闭室组成的牵伸装置——两段合一式拉伸装置,在原有的加热拉伸部分前,增添一个密闭的预热部分,而预热部分的饱和蒸汽温度、湿度和蒸汽压力比加热部分低,使得丝束在加热拉伸前,能进行充分的润湿和加热,从而减少拉伸中产生的毛丝数。通过改进前后三个实验装置对原丝的工艺参数和工艺性的对比,证明了两段合一式拉伸方式,具有不可比拟的优越性,也极大地提高了原丝蒸汽拉伸的工艺性,毛丝与断头数大大减轻。
本文通过X射线衍射、扫描电镜、声速法以及单丝拉伸等测试手段,测试了实验原丝的强度、断裂伸长率、密度、沸水收缩率、结晶度、取向度和晶粒尺寸等参数。系统研究了饱和蒸汽牵伸对PAN原丝结构与性能的影响。结果表明,加热段蒸汽压为5 kg/cm~(2),同管两段不同牵伸域的压力差在2kg/cm~(2)时,原丝的各项力学性能都达到最佳。
由X-射线衍射得到的原丝结晶度随着拉伸倍数的增加而增加,而晶面间距没有太大的变化;由声速法和X-射线衍射法测定的取向度均随着拉伸程度的增加而提高;纤维沸水收缩率的变化研究,发现纤维的内应力与牵伸的倍数和温度有关。而适当控制牵伸过程中的张力和湿度的大小,可以提高纤维的力学性能。扫描电镜的图片的对比表明,两段合一式饱和蒸汽牵伸装置制得的原丝直径更均匀,表面平整且沟槽清晰、细致和均匀,具有更为优化的微观结构。在三种拉伸方式的对比中结果均表明:两段合一式拉伸方式的原丝具有更加优越的结构性能。为现有原丝生产工艺的改进,为高性能的碳纤维原丝的制备创造了有利的条件。
PAN fiber is the key precursor of the high-performance carbon fiber preparation,which has a significant impact on carbon fiber.The PAN precursor's low quality is the bottleneck that hinders the development of carbon fiber in China.Therefore,research on the relationship between PAN filament spinning process and the fiber properties has great significance for improving and enhancing the performance of the carbon fibers.
Because the macromolecular structure of the primary fiber is lack of directional orientation, then its strength is very low.For improving the fiber strength,we need increase its orientation by drawing.The effect of single drafting is limited which could not achieve the mechanical requirement.Therefore,we must use two or multi-level drawing.Drafting the fiber by saturated steam is one of the key technologies to improve the performance of the precursor.However,the technology of this field in our country has many defects,which resulted in the occurrence of broken fiber.
In this paper,X-ray diffraction,scanning electron microscopy,sound velocity method,and single-tow stretch were employed to test experimental precursors' strength,breaking elongation, density,boiling water shrinkage,the degree of crystallinity and orientation,and grain size,etc. Intensive research was carried out on the drafting under the saturated steam's effect on the structure and performance of the PAN.The results showed that the mechanical properties of precursor are best when the vapor pressure is 5 kg/cm~2 and the pressure difference between two different domains in the of drawing tube is 2kg/cm~2.
The crystallinity degree of the precursor was obtained from X-ray diffraction.With the increasing of draw ratio,the crystal space is not changed.The sound velocity method and X-ray diffraction measurement showed that the degree of orientation increased with the growth of tensility.The research on the change rate of fiber boiling water shrinkage indicated that fiber stress was related to the drawing of the multiple and temperature.The proper control of the drawing tension and humidity can increase the fiber mechanical properties.The comparative picture of scanning electron microscope showed that two-one-type saturated steam drawing device can obtain the precursor with uniform diameter,smooth surface and clear groove,as well as a more optimized micro-architecture.The results of the comparison with three stretching modes showed that two-one-type precursor had more superior structure performances.It improved the existing process of PAN precursor production and created proper experiment conditions for the high-performance carbon fiber precursor preparation.
引文
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[4]赵稼祥.世界碳纤维的需求[J],高科技纤维与应用,2005,30(2):7-10.
[5]王延相,王成国,朱波,等.网状和皮芯结构对生产高性能碳纤维组织演变的影响[J],材料科学与工程学报.2005.23(3):325-330.
[6]莫至深,张宏放.晶态聚合物结构和X射线衍射[J],北京:科学出版社,2003:136-229.
[7]Davidson J A,Jung H T,Hudson S D,etc.Investigation of molecular orientation in melt-spun high acrylonitrile fibers[J],Polymer,2000,41:3357-3364.
[8]张旺玺.聚丙烯腈基碳纤维的新进展[J],高科技纤维与应用,2001,26(5):12-14.
[9]Wang Z Q,Zhou A Q,Pen S N,etc.Structure and properties of melt-spun high acrylonitrile copolymer fibers via continuous zone-drawing and zone-annealing processes[J],Thermochimica Acta,2003,396:87-96.
[10]贺福,杨永岗.突破碳纤维产业化的“瓶颈”原丝已是当务之急[J],高科技纤维与应用,2001,26(6):1-5.
[11]贺福,杨永岗,王润娥.用SEM研究PAN基碳纤维的表面缺陷[J],高科技纤维与应用,2002,27:25-29.
[12]张旺玺.提高聚丙烯腈原丝及其碳纤维质量的研究[J],上海纺织科技,2004,32(6):11-14.
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