PAN基预氧丝在碳化过程中的工艺及物化行为研究
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摘要
在PAN基碳纤维的制备过程中,预氧丝的碳化是决定碳纤维质量的关键工艺之一。针对国产原丝开展预氧丝碳化过程的基础性科学研究,深入了解预氧丝在碳化过程中的物理化学变化,明确结构演变规律,探讨工艺、结构及性能的相互关系,可为高性能碳纤维的制备提供理论指导。本文针对自产原丝,在预氧化碳化中试实验线上开展一系列的预氧化、碳化实验,利用差示扫描量热仪(DSC)、热重分析仪(TG)、傅立叶变换红外光谱仪(FTIR)、元素分析仪(EA)、X射线衍射仪(XRD)、电子顺磁共振波谱仪(EPR)、显微激光拉曼光谱仪(LRS)以及高分辨透射电镜(HRTEM)等测试技术,在确定预氧丝制备工艺并制备出适于碳化的预氧丝的基础上,对预氧丝碳化过程中的热行为、结构遗传与演变规律进行全面深入的研究,并探讨了碳化工艺对碳纤维性能的影响。
在碳化研究用预氧丝的制备工艺探讨中,通过在线预氧化实验和对预氧丝样品的表征,综合考虑原丝的放热特性、预氧丝氧含量值随温度的变化增量、有机官能团变化、密度、芳构化度、皮芯结构等多种因素和指标,确定了预氧化的起始温度、最高温度、走丝速度、梯度温度分布以及牵伸等工艺参数,制备了可生产出T300水平碳纤维的预氧丝用以碳化研究。
预氧丝在碳化过程中的热行为研究表明,预氧丝在低温碳化阶段发生放热反应,在高温碳化阶段发生吸热反应。低温碳化放热是结构中的氧元素促进共轭、芳构化及交联等反应的结果,具有进一步稳定纤维结构的作用。预氧丝的预氧化程度、加热气氛以及加热速率都会对低温碳化放热产生影响。高温碳化吸热则是纤维不稳定结构的剧烈裂解反应造成的,与预氧丝的氧含量及预氧化程度密切相关。进一步的研究表明,惰性气氛中对预氧丝的低温碳化处理优于空气中的处理;低温碳化慢速加热使纤维低温放热反应充分进行,有利于纤维高温碳收率的增加;预氧丝结构中的氧元素对于高强碳纤维的制备有重要作用,它既能增加结构稳定性,避免高温剧烈吸热反应发生,又促进了高温裂解反应提前发生,使纤维更易碳化。
应用FTIR、XRD以及LRS实验技术,进一步明确了预氧丝的结构。从化学结构角度,预氧丝大分子链主要由线形链段连接的多个芳构梯形链段组成,并伴有分子链间和链内的交联,而梯形链段是由芳化极不完全的2～4个芳构杂环组成;从物相结构角度,预氧丝由占绝大多数的非晶、少量线形链段有序区以及少量梯形链段有序区组成,而梯形链段有序结构是碳纤维乱层石墨微晶的雏形。
通过对低温、中温及高温不同温度碳化纤维的FTIR、EA、XRD、EPR和LRS表征,研究了预氧丝在两段梯度升温碳化过程中的结构演变。根据结构演变特点,可将整个梯度升温碳化过程分为三个阶段。第一个阶段为300～450℃的纤维结构深入稳定化阶段,此阶段交联和芳构化反应发生,造成含氧模式重排、纤维芳构化度和致密性提高。此时纤维仍由线形链段和梯形链段两部分组成,但前者逐渐减少,后者增多。第二阶段为450～750℃的芳环平面长大并向碳基面转变阶段,线形链段在此阶段发生大规模无规裂解,产生大量自由基;裂解后,纤维主要由芳构化结构组成,随温度的提高,芳构平面逐步长大,并向碳基面转变;同时发生的结构重排,使存在于非晶中的微晶有序区尺寸进一步增大。第三阶段为1000～1400℃的乱层石墨微晶形成并长大阶段,此阶段纤维中的非碳元素排出,碳基面迅速长大并发生剧烈重排形成乱层石墨微晶;到1400℃,结晶度近50%,但微晶仍不完善,边缘存在大量缺陷。
采用HRTEM技术观察了预氧丝和不同碳化温度处理后的碳化纤维研磨碎片的微观组织结构,揭示碳化温度对纤维精细结构的影响。结果表明,不同温度碳化处理的纤维的HRTEM图像各具特点。预氧丝的HRTEM图像是典型的非晶无序点状衬度,反映出预氧丝的非晶结构。低温600℃碳化纤维的皮层HRTEM图像由择优取向的小线段和无序点状衬度共混组成,表明此温度碳化纤维是小尺寸多环平面或碳基面组成的相对有序结构与非晶的共混体,是介于非晶和多晶间的局部有序的过渡态;芯部图像中的小线段没有择优取向。高温1000℃碳化后纤维的皮层HRTEM图像主要由弯折的、沿轴向择优取向的带状条纹组成。带状条纹十几纳米长,由2～5个条纹组成,是乱层堆叠石墨层面衍射产生。其分布不均匀,反映层面堆叠的不规整性。芯部带状条纹形态各异,没有沿轴向择优取向。高温1400℃碳化纤维的皮层HRTEM图像中带状条纹变长变宽,有重叠、交联、缠绕现象,是典型的乱层石墨条带组织。芯部条纹碎小,没有形成明显带状。
各阶段纤维的HRTEM图像清晰的表明了精细组织结构的演变过程。非晶的预氧丝经中低温碳化后,线形链段裂解,梯形链段缩聚形成尺寸极小的多环平面或碳基面,重排后形成沿轴向取向的相对有序区,分布于非晶间。再经高温1000℃碳化,轴向上相邻的但不在同一平面的多环平面或碳基面呈一定夹角头尾相连形成更长碳平面,垂直轴向方向更多层面堆叠,尺寸较小的乱层石墨微晶形成。更高温1400℃碳化时,乱层石墨微晶可能以三种形式长大。在垂直轴向方向,两个相邻并近似平行的乱层石墨微晶可能合并在一起形成更大微晶;而不相平行的两组微晶层面经结构重排后可能发生部分合并。在轴向方向,相邻的微晶条带头尾相接形成更长的条带,乱层石墨微晶迅速长大。在整个碳化过程中,非晶部分或者发生晶化转变为乱层石墨微晶,或者发生裂解以小分子形式从纤维结构中排出,或者仍然存在于碳纤维乱层石墨微晶的边缘或之间。
以三个结构演变阶段为基础设计梯度温度实验,系统而全面的研究了低温、中温和高温碳化温度对纤维强度的影响。实验结果表明,400℃以下的低温碳化处理会加剧纤维的皮芯结构,不利于高强碳纤维的制备;而预先进行500℃的低温碳化处理则有利于碳纤维抗拉强度的提高。500～750℃的中温碳化实验表明,碳纤维抗拉强度在750℃达到最大值。高温碳化时,碳纤维的抗拉强度在1200℃以下快速增加,在1200℃以上缓慢增加。正负牵伸碳化对比实验反映出牵伸在碳纤维制备过程中的重要作用,适当的中低温碳化牵伸可以抑制低温阶段的纤维热收缩,保持并完善预氧化阶段建立的取向,有益于碳纤维抗拉强度的提高;而高温阶段负牵伸的大小也会影响碳纤维的抗拉强度。可以通过在线张力值来判断当前所应用的牵伸是否合适。通过大量实验,发现对于自产1K原丝,所施加的牵伸力使纤维的中低温碳化在线张力保持于150cN/dtex,高温碳化在线张力保持于200～300cN/dtex时得到的碳纤维性能较好。
Carbonization of the stabilized fiber is one of the essential processes which determine the quality of the resulting carbon fiber during the preparation of the polyacrylonitrile (PAN) -based carbon fiber. In order to obtain high quality carbon fibers, it is important to carry out deeply study on the carbonization of the stabilized fiber. The researches on the physical and chemical changes, structure evolution, as well as the relation between processing, structure and properties during carbonization can provide academic help for the preparation of the high-quality carbon fiber. In this work, a series of stabilization and carbonization experiments were performed on a pilot line by using home precursor fiber as the raw material fiber. The stabilized fibers which can be used for carbonization study were prepared by exploring the stabilization processing parameters. Then, the thermal behavior and structure evolution of the stabilized fiber during carbonization were investigated in detail. Several technologies, such as differential scanning calorimetry (DSC), thermal gravimetry (TG), Fourier transform infrared spectroscopy (FTIR), elemental analyzer (EA), X-ray diffraction (XRD), electronic spinning resonance spectrom (EPR) and high resolution transmission electron microscopy (HRTEM) were used to systemically characterize the structure and feature of the samples. At the same time, the influences of processing conditions on the changes of the properties of carbon fibers were also discussed.
The stabilization processing parameters, such as the initial temperature, the highest temperature, the temperature gradient distribution, the running speed and the stretching ratio were confirmed by consider systematically the various stabilization indices and factors, like exothermic property of the PAN fiber, the oxygen content increment of the stabilized fiber with raising stabilization temperature, the density, aromatization extent and skin-core structure of the stabilized fiber, and so on. The stabilized fiber which can produce the T300-level carbon fiber were prepared by using the optimal stabilization processing parameters. These stabilized fiber were carbonized further for carrying out the carbonization study.
The investigation on the thermal behavior of the stabilized fiber during carbonization shows that the exothermal reactions happen when the stailized fiber was carbonized at low temperature, while endothermal reactions appear at high-termperature carbonization stage. The heat liberation at low-temperature carbonization stage is the result of conjugation reaction, aromatization reaction and cross-linking reaction which are facilitated by the oxygen element of the stabilized fiber. These exothermic reactions further stabilize the strcutre of the stabilized fiber. Additionally, the stabilization extent of the stabilized fiber, the heat treatment atmosphere and the heating rate all have effects on the exotherm of the fiber. The endothermal peak and endothermic quantity during high-temperature carbonization, which are reduced by the pyrolysis of the unstable structure, are closely related to the oxygen content and stabilization extent of the stabilized fiber. The further studies indicate that the heating treatment in oxygen-free atomosphere is better than that in air; the heating treatment at low velocity during low-temperature carbonization is beneficial to the increasing of the yield of the carbon fiber; the oxygen element in stabilized fiber is important to the preparation of the high-quality carbon fiber, because it not only can increase the stability of the structure and avoid the hard endothermic reactions, but also can facilitate the pyrolysis reaction to start as early as possible.
The structure of the stabilized fiber was further studied by FTIR, XRD and LRS. From the view of the chemical structure, the macromolecules of the stabilized fiber are composed of some aromatized ladder segments which are connected by linear segments, accompanying the intro- and inter-molecular cross-linking; the aromatized ladder segment is composed of 2-4 aromatization cycles. From the view of the phase structure, the stabilized fiber is constitutive of the most amorphous structure, a few linear segments order regions and a few aromatized ladder segments order regions.
The study on the structure evolution of the stabilized fiber during two-step carbonization by FTIR, EA, XRD, EPR and LRS indicates that the total carbonization process can be divided into three stages. The first is the further stability stage of the fiber structure at 300～450℃. At this stage, the exothermal reactions like cross-linking reaction and aromatization reaction happen, which can improve the stability of the fiber structure and result in the increase of the aromatization extent and compactability. The structure of the fiber still consists of linear segments and ladder polymer segments; but the former gradually reduces and the latter increases. The second stage is at 450～750℃, during which the aromatization plane grows and converts to the carbon basal plane. The linear segments pyrolyzes inregularly in large scale to produce much free radicals. The pyrolysis reaction happens in short time and produce a great deal of free radicals. After pyrolysis, the fiber is mainly compose of the ladder aromatization structures which convert gradually into carbon basal planes with raise of the temperature. The third stage is at 100-1400℃, during which turbo graphite micro-cystal forms and grows. The non-carbon elements are taken off from the fiber and the turbo graphite structure form resulted from the growth of the carbon basal planes. Till 1400℃, the crystallinity of the carbon fiber is nearly up to 50%. However, there are mass structure defects lying in the edge of the graphite planes or between graphite planes, indicating that the graphite crystalline region is not perfect.
The microstructure of the stabilized fiber and the carbonized fiber at different temperature were observed and the effects of the carbonization temperature on the fine structure of the fiber were explored. The experimental results show that the HRTEM images of the stabilized fiber present typical amorphous disorder maze-like clusters, which reflects the amorphous structure of the fiber. After carbonized at 600℃, the HRTEM images of the skin of the fiber are the complex of the line section with preferred orientation and amorphous. The line section is produced by the diffraction of the tiny poly-cyclic plane or the carbon basal plane. However, the line section in the core of the fiber is without preferred orientation. There are some bend ribbon-like fringes appearing in the HRTEM image of the skin of the carbonized fiber after treated at 1000℃. The ribbon-like fringes are more than 10 nm in length and include 2-5 fringes in width, producing by the diffraction of the turbo graphite micro-crystall planes. Whereas, the ribbon-like fringes in the core of the fiber is anisotropic, without preferred orientation. The ribbon-like fringes become longer and wider with the increase of treatment temperature from 1000℃to 1400℃. There are the overlap, cross-linking and intertwist between ribbon-like fringes. The fringes in the core of the fiber are tiny, without forming the ribbon.
The formation process of the turbo graphite ribbon structure during carbonization is reflected by the HRTEM images. After the amorphous stabilized fiber was carbonized at medium-temperatuer carbonization temperature, the ladder segments condense into the poly-cyclic planes or carbon basal plane. Their reorganization bring the formation of the relative order region with axial orientation. After carbonized at 1000℃, the adjacent poly-cyclic planes or carbon basal plane connect together head-to-head to form longer carbon planes in the axial direction and more planes stack in the radial direction. So, the turbo graphite micro-cystals form. When the fiber was carbonized at 140Q℃, the crystal regions grow by three styles, which can be speculated from the morphorlogy of the ribbon-like fringes in the HRTEM images. One is two adjacent and parallel crystal regions combine together after reorganization in the direction of the axis; The second is the adjacent but unparallel crystal regions combine partially. And the third is the adjacent crystal ribbons connect together head-to-head to form longer ribbon in the radial direction, which brings the quick growth of the crystal region.
The tensile strength of the carbon fiber can be greatly improved by adjusting the carbonization gradient temperature. The temperature gradient experiments were carried out in the three stages of structure evolution, respectively. The experimental results shows that the pre-carbonization treatment at 500℃is benefit to the improvement of the quality of the carbon fiber. However, the pre-treatment at 400℃is harmful to the preparation of the carbon fiber because the cross-linking reaction lows the the order of the fiber structure and aggravate the skin-core structure. In the experimatal range from 500℃to 700℃, the increase of the temperature can improve the tensile strength of the carbon fiber. In the high-temperature carbonization stage, the formation speed, quantity and crystal size of the turbo graphite structure quickly increase with raising temperature below 1200℃and then slowly grow above 1200℃. Accordingly, the tensile strength of the carbon fiber increase quickly at first below 1200℃and then slowly above 1200℃. The proper stretching ratio during low-temperature carbonization can restrain the thermal shrinkage, which can retain and perfect the orientation of the ladder polymer. The appropriate relax also effect on the strength of the carbon fiber. The on-line tension values can be used to judge whether the current stretching ratio applied is proper. The high-quality carbon fiber can be obtained when the on-line tension at pre-carbonization stage lies 150 cN/dtex or so, while the on-line tension at high-temperature carbonization stage lies 200-300 cN/dtex.
在碳化研究用预氧丝的制备工艺探讨中,通过在线预氧化实验和对预氧丝样品的表征,综合考虑原丝的放热特性、预氧丝氧含量值随温度的变化增量、有机官能团变化、密度、芳构化度、皮芯结构等多种因素和指标,确定了预氧化的起始温度、最高温度、走丝速度、梯度温度分布以及牵伸等工艺参数,制备了可生产出T300水平碳纤维的预氧丝用以碳化研究。
预氧丝在碳化过程中的热行为研究表明,预氧丝在低温碳化阶段发生放热反应,在高温碳化阶段发生吸热反应。低温碳化放热是结构中的氧元素促进共轭、芳构化及交联等反应的结果,具有进一步稳定纤维结构的作用。预氧丝的预氧化程度、加热气氛以及加热速率都会对低温碳化放热产生影响。高温碳化吸热则是纤维不稳定结构的剧烈裂解反应造成的,与预氧丝的氧含量及预氧化程度密切相关。进一步的研究表明,惰性气氛中对预氧丝的低温碳化处理优于空气中的处理;低温碳化慢速加热使纤维低温放热反应充分进行,有利于纤维高温碳收率的增加;预氧丝结构中的氧元素对于高强碳纤维的制备有重要作用,它既能增加结构稳定性,避免高温剧烈吸热反应发生,又促进了高温裂解反应提前发生,使纤维更易碳化。
应用FTIR、XRD以及LRS实验技术,进一步明确了预氧丝的结构。从化学结构角度,预氧丝大分子链主要由线形链段连接的多个芳构梯形链段组成,并伴有分子链间和链内的交联,而梯形链段是由芳化极不完全的2～4个芳构杂环组成;从物相结构角度,预氧丝由占绝大多数的非晶、少量线形链段有序区以及少量梯形链段有序区组成,而梯形链段有序结构是碳纤维乱层石墨微晶的雏形。
通过对低温、中温及高温不同温度碳化纤维的FTIR、EA、XRD、EPR和LRS表征,研究了预氧丝在两段梯度升温碳化过程中的结构演变。根据结构演变特点,可将整个梯度升温碳化过程分为三个阶段。第一个阶段为300～450℃的纤维结构深入稳定化阶段,此阶段交联和芳构化反应发生,造成含氧模式重排、纤维芳构化度和致密性提高。此时纤维仍由线形链段和梯形链段两部分组成,但前者逐渐减少,后者增多。第二阶段为450～750℃的芳环平面长大并向碳基面转变阶段,线形链段在此阶段发生大规模无规裂解,产生大量自由基;裂解后,纤维主要由芳构化结构组成,随温度的提高,芳构平面逐步长大,并向碳基面转变;同时发生的结构重排,使存在于非晶中的微晶有序区尺寸进一步增大。第三阶段为1000～1400℃的乱层石墨微晶形成并长大阶段,此阶段纤维中的非碳元素排出,碳基面迅速长大并发生剧烈重排形成乱层石墨微晶;到1400℃,结晶度近50%,但微晶仍不完善,边缘存在大量缺陷。
采用HRTEM技术观察了预氧丝和不同碳化温度处理后的碳化纤维研磨碎片的微观组织结构,揭示碳化温度对纤维精细结构的影响。结果表明,不同温度碳化处理的纤维的HRTEM图像各具特点。预氧丝的HRTEM图像是典型的非晶无序点状衬度,反映出预氧丝的非晶结构。低温600℃碳化纤维的皮层HRTEM图像由择优取向的小线段和无序点状衬度共混组成,表明此温度碳化纤维是小尺寸多环平面或碳基面组成的相对有序结构与非晶的共混体,是介于非晶和多晶间的局部有序的过渡态;芯部图像中的小线段没有择优取向。高温1000℃碳化后纤维的皮层HRTEM图像主要由弯折的、沿轴向择优取向的带状条纹组成。带状条纹十几纳米长,由2～5个条纹组成,是乱层堆叠石墨层面衍射产生。其分布不均匀,反映层面堆叠的不规整性。芯部带状条纹形态各异,没有沿轴向择优取向。高温1400℃碳化纤维的皮层HRTEM图像中带状条纹变长变宽,有重叠、交联、缠绕现象,是典型的乱层石墨条带组织。芯部条纹碎小,没有形成明显带状。
各阶段纤维的HRTEM图像清晰的表明了精细组织结构的演变过程。非晶的预氧丝经中低温碳化后,线形链段裂解,梯形链段缩聚形成尺寸极小的多环平面或碳基面,重排后形成沿轴向取向的相对有序区,分布于非晶间。再经高温1000℃碳化,轴向上相邻的但不在同一平面的多环平面或碳基面呈一定夹角头尾相连形成更长碳平面,垂直轴向方向更多层面堆叠,尺寸较小的乱层石墨微晶形成。更高温1400℃碳化时,乱层石墨微晶可能以三种形式长大。在垂直轴向方向,两个相邻并近似平行的乱层石墨微晶可能合并在一起形成更大微晶;而不相平行的两组微晶层面经结构重排后可能发生部分合并。在轴向方向,相邻的微晶条带头尾相接形成更长的条带,乱层石墨微晶迅速长大。在整个碳化过程中,非晶部分或者发生晶化转变为乱层石墨微晶,或者发生裂解以小分子形式从纤维结构中排出,或者仍然存在于碳纤维乱层石墨微晶的边缘或之间。
以三个结构演变阶段为基础设计梯度温度实验,系统而全面的研究了低温、中温和高温碳化温度对纤维强度的影响。实验结果表明,400℃以下的低温碳化处理会加剧纤维的皮芯结构,不利于高强碳纤维的制备;而预先进行500℃的低温碳化处理则有利于碳纤维抗拉强度的提高。500～750℃的中温碳化实验表明,碳纤维抗拉强度在750℃达到最大值。高温碳化时,碳纤维的抗拉强度在1200℃以下快速增加,在1200℃以上缓慢增加。正负牵伸碳化对比实验反映出牵伸在碳纤维制备过程中的重要作用,适当的中低温碳化牵伸可以抑制低温阶段的纤维热收缩,保持并完善预氧化阶段建立的取向,有益于碳纤维抗拉强度的提高;而高温阶段负牵伸的大小也会影响碳纤维的抗拉强度。可以通过在线张力值来判断当前所应用的牵伸是否合适。通过大量实验,发现对于自产1K原丝,所施加的牵伸力使纤维的中低温碳化在线张力保持于150cN/dtex,高温碳化在线张力保持于200～300cN/dtex时得到的碳纤维性能较好。
Carbonization of the stabilized fiber is one of the essential processes which determine the quality of the resulting carbon fiber during the preparation of the polyacrylonitrile (PAN) -based carbon fiber. In order to obtain high quality carbon fibers, it is important to carry out deeply study on the carbonization of the stabilized fiber. The researches on the physical and chemical changes, structure evolution, as well as the relation between processing, structure and properties during carbonization can provide academic help for the preparation of the high-quality carbon fiber. In this work, a series of stabilization and carbonization experiments were performed on a pilot line by using home precursor fiber as the raw material fiber. The stabilized fibers which can be used for carbonization study were prepared by exploring the stabilization processing parameters. Then, the thermal behavior and structure evolution of the stabilized fiber during carbonization were investigated in detail. Several technologies, such as differential scanning calorimetry (DSC), thermal gravimetry (TG), Fourier transform infrared spectroscopy (FTIR), elemental analyzer (EA), X-ray diffraction (XRD), electronic spinning resonance spectrom (EPR) and high resolution transmission electron microscopy (HRTEM) were used to systemically characterize the structure and feature of the samples. At the same time, the influences of processing conditions on the changes of the properties of carbon fibers were also discussed.
The stabilization processing parameters, such as the initial temperature, the highest temperature, the temperature gradient distribution, the running speed and the stretching ratio were confirmed by consider systematically the various stabilization indices and factors, like exothermic property of the PAN fiber, the oxygen content increment of the stabilized fiber with raising stabilization temperature, the density, aromatization extent and skin-core structure of the stabilized fiber, and so on. The stabilized fiber which can produce the T300-level carbon fiber were prepared by using the optimal stabilization processing parameters. These stabilized fiber were carbonized further for carrying out the carbonization study.
The investigation on the thermal behavior of the stabilized fiber during carbonization shows that the exothermal reactions happen when the stailized fiber was carbonized at low temperature, while endothermal reactions appear at high-termperature carbonization stage. The heat liberation at low-temperature carbonization stage is the result of conjugation reaction, aromatization reaction and cross-linking reaction which are facilitated by the oxygen element of the stabilized fiber. These exothermic reactions further stabilize the strcutre of the stabilized fiber. Additionally, the stabilization extent of the stabilized fiber, the heat treatment atmosphere and the heating rate all have effects on the exotherm of the fiber. The endothermal peak and endothermic quantity during high-temperature carbonization, which are reduced by the pyrolysis of the unstable structure, are closely related to the oxygen content and stabilization extent of the stabilized fiber. The further studies indicate that the heating treatment in oxygen-free atomosphere is better than that in air; the heating treatment at low velocity during low-temperature carbonization is beneficial to the increasing of the yield of the carbon fiber; the oxygen element in stabilized fiber is important to the preparation of the high-quality carbon fiber, because it not only can increase the stability of the structure and avoid the hard endothermic reactions, but also can facilitate the pyrolysis reaction to start as early as possible.
The structure of the stabilized fiber was further studied by FTIR, XRD and LRS. From the view of the chemical structure, the macromolecules of the stabilized fiber are composed of some aromatized ladder segments which are connected by linear segments, accompanying the intro- and inter-molecular cross-linking; the aromatized ladder segment is composed of 2-4 aromatization cycles. From the view of the phase structure, the stabilized fiber is constitutive of the most amorphous structure, a few linear segments order regions and a few aromatized ladder segments order regions.
The study on the structure evolution of the stabilized fiber during two-step carbonization by FTIR, EA, XRD, EPR and LRS indicates that the total carbonization process can be divided into three stages. The first is the further stability stage of the fiber structure at 300～450℃. At this stage, the exothermal reactions like cross-linking reaction and aromatization reaction happen, which can improve the stability of the fiber structure and result in the increase of the aromatization extent and compactability. The structure of the fiber still consists of linear segments and ladder polymer segments; but the former gradually reduces and the latter increases. The second stage is at 450～750℃, during which the aromatization plane grows and converts to the carbon basal plane. The linear segments pyrolyzes inregularly in large scale to produce much free radicals. The pyrolysis reaction happens in short time and produce a great deal of free radicals. After pyrolysis, the fiber is mainly compose of the ladder aromatization structures which convert gradually into carbon basal planes with raise of the temperature. The third stage is at 100-1400℃, during which turbo graphite micro-cystal forms and grows. The non-carbon elements are taken off from the fiber and the turbo graphite structure form resulted from the growth of the carbon basal planes. Till 1400℃, the crystallinity of the carbon fiber is nearly up to 50%. However, there are mass structure defects lying in the edge of the graphite planes or between graphite planes, indicating that the graphite crystalline region is not perfect.
The microstructure of the stabilized fiber and the carbonized fiber at different temperature were observed and the effects of the carbonization temperature on the fine structure of the fiber were explored. The experimental results show that the HRTEM images of the stabilized fiber present typical amorphous disorder maze-like clusters, which reflects the amorphous structure of the fiber. After carbonized at 600℃, the HRTEM images of the skin of the fiber are the complex of the line section with preferred orientation and amorphous. The line section is produced by the diffraction of the tiny poly-cyclic plane or the carbon basal plane. However, the line section in the core of the fiber is without preferred orientation. There are some bend ribbon-like fringes appearing in the HRTEM image of the skin of the carbonized fiber after treated at 1000℃. The ribbon-like fringes are more than 10 nm in length and include 2-5 fringes in width, producing by the diffraction of the turbo graphite micro-crystall planes. Whereas, the ribbon-like fringes in the core of the fiber is anisotropic, without preferred orientation. The ribbon-like fringes become longer and wider with the increase of treatment temperature from 1000℃to 1400℃. There are the overlap, cross-linking and intertwist between ribbon-like fringes. The fringes in the core of the fiber are tiny, without forming the ribbon.
The formation process of the turbo graphite ribbon structure during carbonization is reflected by the HRTEM images. After the amorphous stabilized fiber was carbonized at medium-temperatuer carbonization temperature, the ladder segments condense into the poly-cyclic planes or carbon basal plane. Their reorganization bring the formation of the relative order region with axial orientation. After carbonized at 1000℃, the adjacent poly-cyclic planes or carbon basal plane connect together head-to-head to form longer carbon planes in the axial direction and more planes stack in the radial direction. So, the turbo graphite micro-cystals form. When the fiber was carbonized at 140Q℃, the crystal regions grow by three styles, which can be speculated from the morphorlogy of the ribbon-like fringes in the HRTEM images. One is two adjacent and parallel crystal regions combine together after reorganization in the direction of the axis; The second is the adjacent but unparallel crystal regions combine partially. And the third is the adjacent crystal ribbons connect together head-to-head to form longer ribbon in the radial direction, which brings the quick growth of the crystal region.
The tensile strength of the carbon fiber can be greatly improved by adjusting the carbonization gradient temperature. The temperature gradient experiments were carried out in the three stages of structure evolution, respectively. The experimental results shows that the pre-carbonization treatment at 500℃is benefit to the improvement of the quality of the carbon fiber. However, the pre-treatment at 400℃is harmful to the preparation of the carbon fiber because the cross-linking reaction lows the the order of the fiber structure and aggravate the skin-core structure. In the experimatal range from 500℃to 700℃, the increase of the temperature can improve the tensile strength of the carbon fiber. In the high-temperature carbonization stage, the formation speed, quantity and crystal size of the turbo graphite structure quickly increase with raising temperature below 1200℃and then slowly grow above 1200℃. Accordingly, the tensile strength of the carbon fiber increase quickly at first below 1200℃and then slowly above 1200℃. The proper stretching ratio during low-temperature carbonization can restrain the thermal shrinkage, which can retain and perfect the orientation of the ladder polymer. The appropriate relax also effect on the strength of the carbon fiber. The on-line tension values can be used to judge whether the current stretching ratio applied is proper. The high-quality carbon fiber can be obtained when the on-line tension at pre-carbonization stage lies 150 cN/dtex or so, while the on-line tension at high-temperature carbonization stage lies 200-300 cN/dtex.
引文
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