PAN原丝至碳纤维缺陷的形成与遗传性

利用扫描电镜（SEM）研究了聚丙烯腈（PAN）原丝至碳纤维结构形态转化过程中缺陷的形成与遗传,结果表明,PAN初生纤维,原丝,预氧化纤维和碳纤维的表面缺陷主要包括沟槽,横纹,粘丝、并丝、杂质、划伤和孔洞等,PAN初生纤维和原丝的内部缺陷主要是皮芯结构、芯部疏松和孔洞,皮芯结构由凝固浴中纤维的双扩散所导致,一直保留到原丝、预氧化纤维直到碳纤维中,可以通过调整凝固的工艺参数增大原丝皮层比例,提高芯部致密性,内部孔洞的形成与扩散和相分离速率有关,可以通过改善致密化和蒸汽拉伸工艺来减少孔洞和减小孔洞尺寸,预氧化纤维中的皮芯结构的形成归因于原丝的遗传和氧的不均匀扩散.     

硼酸改性PAN原丝提高预氧化纤维的均质化程度

利用硼酸浸渍PAN原丝,然后进行原丝预氧化,最后制得了致密化程度高的预氧化纤维。利用扫描电子显微镜(SEM)、X射线衍射(XRD)和傅里叶变换红外光谱(FTIR)对预氧化纤维的形貌、结构和结晶度进行了分析研究。研究表明,硼酸改性能降低环化度,提高致密化程度,从而获得均质的预氧化纤维。     

碳纳米管/聚丙烯腈复合纤维的制备及结构研究

通过原位聚合的方法制备了碳纳米管/聚丙烯腈(CNTs/PAN)聚合液,用湿法纺丝工艺制备了CNTs/PAN复合纤维,分析了复合纤维流变性能、热性能及截面形貌。结果表明:CNTs的加入使得聚合物溶液出现了假凝胶化,粘度和弹性均有所上升,纺丝时溶液细流的表层遇水迅速凝固成致密的皮层,影响了纤维芯部的二甲基亚砜(DMSO)和水的双扩散作用,凝固丝出现了很明显的皮芯结构,CNTs的加入还使得纤维预氧化放热过程得到了缓和。     

张力对PAN预氧化纤维结构和性能的影响

在预氧化过程中通过施加不同张力制备了四组PAN预氧化纤维,并利用单纤维强力测试仪、元素分析仪、X射线衍射仪、扫描电子显微镜等对PAN基碳纤维原丝及预氧化纤维的力学性能、微观结构和表面形貌进行了研究。结果表明,热处理过程中负载张力的增加会引起预氧化纤维表面形貌发生明显变化,预氧化纤维表面整体更加光滑,其(002)晶面的晶粒尺寸变大,微晶择优取向程度增加,预氧化纤维中C元素含量逐渐降低,O元素含量逐渐增加,预氧化纤维的拉伸强度、拉伸模量、断裂伸长率都呈现逐渐降低的趋势。     

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。     

两种PAN原丝油剂在碳纤维生产过程中的作用机理探讨

通过比较两种PAN原丝油剂的理化特性,对原丝性能、预氧纤维皮芯结构、碳纤维灰分等进行了分析,探讨了两种油剂在碳纤维生产过程中的作用机理。结果表明,包覆型碳纤维原丝油剂在原丝表面形成一层包覆层并较少的渗透到纤维内部,控制了预氧化阶段氧和能量向纤维内部的径向扩散速率,包覆层在预氧化与低温碳化阶段更容易脱落和排出,减少了纤维缺陷的产生,更好的保护了纤维的皮部结构且使碳纤维的灰分质量分数更低。     

磁场对聚丙烯腈原丝及其预氧化的影响

在加热条件下对聚丙烯腈(PAN)原丝施加强磁场,研究了磁场对PAN原丝的影响及经过强磁场预处理后的PAN原丝在预氧化过程中产生的变化;采用红外吸收光谱、X射线衍射、扫描电子显微镜等方法对PAN原丝进行表征。结果表明:经磁场强度为1.9 T,磁化时间为60 min的磁场预处理后,PAN原丝的氰基基团取向度从0.37增大到0.46,微晶尺寸减小12.95%,相同预氧化温度下的相对环化率均大幅提高,纤维密度均有增大,预氧化丝的皮芯结构明显改善。     

PAN纤维上油量对预氧化纤维结构和性能的影响

本研究以两种上油量PAN纤维为研究对象,采用示差扫描量热仪(DSC)、红外光谱(FTIR)、X射线衍射(XRD)等表征手段,考察了上油量对预氧化纤维结构与性能之间的关联。不同上油量的PAN原丝在后续的工艺中结构和性能会发生变化,进而对预氧化过程产生影响。结果表明,PAN原丝上油量在1%左右时,预氧化过程中产生的纤维性能较优异。     

聚丙烯腈纤维片层组织结构演变历程的研究

为了研究原丝中片层微观组织的演变性,借助电子显微镜,跟踪了片层组织结构在纺丝、预氧化和炭化过程中所发生的变化。结果发现:原丝由取向不同的片层组织结构构成,形成最终碳纤维后,碳层不会在C轴上做有规则的ABA式堆砌,个别的碳层面绕C轴发生旋转而失去碳层的三维有序结构,仅仅生成二维有序的乱层结构。预氧化纤维有“皮芯结构”,外层由与纤维轴平行或者倾斜成一定角度的微纤片层结构组成,而内部是杂乱无章的片层结构,或者是微小的空隙,皮层的厚薄与预氧化处理方式有关。经过1000℃烧制的碳纤维层片厚度约为0.03~0.10滋m。经过1350℃炭化后所得的纤维,由许多类似鱼鳞的片层构成,片层上有纳米级的微晶。     

聚丙烯腈预氧化纤维碳化中的结构演变与碳纤维微观结构

利用DSC/TG、FT-IR、XRD、元素分析、SEM、TEM和HRTEM系统研究了聚丙烯腈预氧化纤维碳化中的结构演变与碳纤维微观结构。结果表明,中温碳化时,未环化的—C≡N基团继续反应。高温碳化进一步脱H、脱N形成C六元环结构。T-700碳纤维的002衍射峰强度明显高于自制碳纤维,层面间距d₀₀₂小、石墨网堆叠厚度L_c大、结晶度高。碳纤维呈皮芯结构,表皮由片层堆叠而成,结构致密,含大量纳米级微晶的石墨层结构沿纤维轴取向好,而芯部结构疏松。碳纤维皮芯结构的非均质性由原丝和预氧化纤维的结构演变而来。碳纤维分子结构中存在条带结构和球形结构。条带结构的碳层与原丝分子链条带结构状态十分相似。球形结构的碳网面围绕球心排列,与预氧化纤维的球形结构类似,表明原丝至碳纤维的结构转化过程中纤维分子链结构的变化有密切相关性。     

Heredity and difference of multiple-scale microstructures in PAN-based carbon fibers and their precursor fibers

Multiple-scale microstructures, including skin-core structure, fibril structure, lamellar structure, crystal/amorphous structure, were found co-present in the fibers during the whole production process of polyacrylonitrile (PAN)-based carbon fibers. The structural heredity and difference among them were systematically investigated for the first time by scanning electron microscope, optical microscope, transmission electron microscope, and X-ray diffraction. The relations between the four kinds of structures and their formation mechanisms were analyzed. The skin-core structure is contributed to inhomogeneous distribution of composition and chemical structure along the radial direction in oxidative stabilized fibers, which is proved different in PAN precursor fibers and carbon fibers. Fibrils are successively separated from low-temperature oxidative stabilized fibers by ultrasonic etching in dimethylsulfoxide solution. The separation of individual fibril becomes harder and even impossible in those fibers prepared at temperatures higher than 245°C. This suggests a stronger bonding force between fibrils in high-temperature oxidative stabilized fibers and carbon fibers. The lamellar structures within fibrils are observed in all of these fibers but with thicker lamella width with increasing temperature. They are unlikely due to the alternatively alignment of crystal regions and amorphous regions as reported by many previous literature, because the oxidative stabilized fibers are amorphous but have lamellar structures. The (002) diffraction arc gives the evidence that the lamellar structure in carbon fibers is not strictly perpendicular to the fiber axis, but have an angle of about 45° with it. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The influence of continuous stabilization on the properties of stabilized fibers and the final activated carbon fibers. Part I

This study found that, during continuous stabilization and carbonization, the shrinkage behavior of polyacrylonitrile (PAN) fibers affects the morphology and properties of the stabilized fibers, the carbon fibers, and the final activated carbon fibers. In the stabilized fibers, a higher shrinkage of the PAN fibers during the stabilization process increased the oxygen content and the core proportion and decreased the formation of ladder polymers. The effect of the shrinkage behavior of the PAN fibers on the fracture surfaces of the stabilized fibers is discussed. A microstructure model of stabilized fibers is presented, depicting fine radial structure at the fiber center. When stabilized fibers were carbonized during a continuous carbonization process, a hole structure was found in the fiber center at the temperature of 800°C, and a hollow core was found at the temperature of 1300°C. The shrinkage behaviors during the stabilization stage and the formation of the hole and the hollow core in the fiber's center during the carbonization stage are discussed. The carbon fibers developed from shrunk stabilized fibers have a lower density and lower preferred orientation than fibers developed from unshrunk stabilized fibers. But the fibers developed in this new process have greater nitrogen and oxygen content, and have a greater porosity than the traditionally-produced fibers. The mechanical properties df the new and the traditional fibers are comparable. These characteristics are very valuable in the production of activated carbon fibers, which will be described in our next paper.     

Carbon fibers derived from UV‐assisted stabilization of wet‐spun polyacrylonitrile fibers

A rapid, dual‐stabilization route for the production of carbon fibers from polyacrylonitrile (PAN) precursor fibers is reported. A photoinitiator, 4,4′‐bis(diethylamino)benzophenone, was added to PAN solution before the fiber wet‐spinning step. After a short UV treatment that induced cyclization and crosslinking at a lower temperature, precursor fibers could be rapidly thermo‐oxidatively stabilized and successfully carbonized. Scanning electron microscopy micrographs show no deterioration of the microstructure or hollow‐core formation in the fibers due to UV treatment or presence of photoinitiator. Fast‐thermally stabilized pure PAN‐based carbon fibers show hollow‐core fiber defects due to inadequate thermal stabilization, but such defects were not observed in carbon fibers derived from fast‐thermally stabilized fibers that contained photoinitiator and were UV treated. Tensile testing results confirm that fibers containing 1 wt % photoinitiator and UV treated for 5 min display higher tensile modulus than all other sets of thermally stabilized and carbonized fibers. Wide‐angle X‐ray diffraction results show a higher development of the aromatic structure and molecular orientation in thermally stabilized fibers. No significant increase in interplanar spacing or decrease in crystals size were observed within the UV‐stabilized carbon fibers containing photoinitiator, but such fibers retain a higher extent of molecular orientation when compared with control fibers. These results establish for the first time, the positive effect of the external addition of photoinitiator and UV treatment on the properties of the PAN‐based fibers, and may be used to reduce the precursor stabilization time for faster carbon fiber production rate. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40623.     

SEM and OM Study on the Microstructure of Oxidative Stabilized Polyacrylonitrile Fibers

Summary Three polyacrylonitrile fibers were oxidative stabilized by two heat treatment modes. OM and SEM were utilized to analyze the microstructure of oxidative stabilized fibers. In experiment I (by stepwise increasing temperature), no skin-core structure occurs in the polished cross-sections of stabilized fibers from 195 °C to 265 °C, unless they are subsequently heated by temperature higher than 270 °C. In experiment II (by isothermal temperature), the oxidative stabilized fibers heated at 230 °C for 120min shows homogeneous microstructure, but those heated at 250 °C for only 60min displays distinct skin-core morphology. The shape of the boundary between the skin and the core resembles the cross-section shape of precursor fibers, but the thickness of the skin keeps almost unchanged of about 4 μm. With the increasing of temperature, the stiffness of stabilized fibers increases and the evolution of microstructure undergo four steps. It indicated that temperature is the essential factor that affects the skin-core morphology, while the cross-section shape of precursor is irrelevant to that. If fibers are directly heated at high temperature without low temperature treatment, the light colored core will fuse into a hole and deteriorate the properties of carbon fibers.     

Wet‐spun,photoinitiator‐modified polyacrylonitrile precursor fibers: UV‐assisted stabilization

The role of dilute concentrations (～1 wt %) of a photoinitiator, 4,4 ′ ‐bis(diethylamino)benzophenone, on the processability and properties of the resulting wet‐spun polyacrylonitrile (PAN) fibers are reported. Rheology measurements show no adverse effect on the viscosities of solutions by the addition of the photoinitiator. Fibers containing photoinitiator were successfully wet‐spun from PAN – DMSO solution. FTIR results prove that 4,4 ′ ‐bis(diethylamino)benzophenone was retained in the fibers after coagulation and post‐stretching. SEM micrographs show no deterioration of the post‐stretched fiber microstructure due to the presence of photoinitiator. Tensile testing results show a small reduction in the strain‐at‐break of post‐stretched fibers containing photoinitiator when compared with pure (control) PAN fibers. After UV treatment, fibers with 4,4 ′ ‐bis(diethylamino)benzophenone display a higher tensile modulus compared with the other sets. Wide‐angle X‐ray diffraction results show no significant decrease in interplanar spacing and size of the crystals within the fibers containing photoinitiator, but such fibers retain a higher extent of molecular orientation after being UV treated. Conversion indices were measured from the WAXD spectra and compared with conventional thermal stabilized fibers. This correlation confirms that the addition of 1 wt % photoinitiator to PAN followed by 5 min of UV treatment leads to a conversion index that is observed in control fibers after more than an hour, which could reduce the conventional thermo‐oxidative stabilization time significantly. These results indicate the potential of the dual stabilization route in generating precursor fibers with higher molecular orientation, and possibly reducing the thermo‐oxidation time during carbon fiber processing. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2494–2503, 2013     

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。     

大直径中间相沥青基炭纤维的制备研究

以萘系中间相沥青为原料,通过熔融纺丝和随后的预氧化、炭化以及石墨化处理制备了中间相沥青基圆形炭纤维.研究了热处理温度对纤维导电性能和力学性能的影响,并采用红外光谱仪、元素分析仪、扫描电子显微镜和X射线衍射仪对纤维的组成、形貌和微观结构进行了表征.研究结果表明：纤维在预氧化时形成的羟基、酰基等含氧官能团在随后的炭化、石墨化处理过程中消失;随热处理温度的升高,石墨微晶逐渐发育、长大,并沿纤维轴向高度取向,纤维的电阻率不断降低,力学性能不断增强;3 000℃石墨化纤维电阻率为1.3μΩ·m,对应的强度和模量值为1.6GPa和380 GPa.     

Gel-spun carbon nanotubes/polyacrylonitrile composite fibers. Part I: Effect of carbon nanotubes on stabilization

Addition of carbon nanotubes (CNTs) in polyacrylonitrile (PAN) fibers significantly improves the mechanical properties of the resulting carbon fibers. This study focuses on the effect of different types of CNTs on chemical, mechanical and structural changes during the stabilization of gel-spun CNT/PAN composite fibers. Among the different types of CNTs, it was observed that CNTs containing more walls had lower reinforcement efficiency than CNTs containing fewer walls. Similarly CNTs containing fewer walls exhibited higher orientation of the ladder polymer and greater effect on the formation of β-amino nitrile in the stabilized fibers. Wide angle X-ray diffraction, infrared spectroscopy, and scanning electron microscopy were used to determine the optimum stabilization time. Additionally, it was found that the higher tension applied during stabilization improved the properties of the stabilized fibers, and the addition of CNTs increased the maximum tension that the fiber can bear.     

Microstructure difference between core and skin of T700 carbon fibers in heat-treated carbon/carbon composites

The core and skin microstructure of T700 carbon fibers in carbon/carbon composites, prepared with chemical vapor infiltration (CVI) at 1000 °C and heat treated at 2300 and 2800 °C, have been studied by means of high-resolution transmission electron microscopy (HRTEM). The orientation angles of the graphitic basal planes obtained from selected-area electron-diffraction patterns show that the structure difference between the core and skin is a change of the degree of preferred orientation of the graphitic basal planes which decreases gradually from the skin region to the core region after CVI at 1000 °C. With increasing heat-treatment temperature, the basal planes orient parallel to the fiber axis, first in the skin region and then in the core region. In addition, the diameter of the core region decreases considerably from about 3.3 to 2.2 μm after heat treatment at 2800 °C. HRTEM lattice-fringe images show that the graphitic crystallite size increases significantly both in the core and skin, but more in the skin. Moreover, with increasing crystallite size, pores of nanometer scale start to form in the fiber.     

The skin‐core structure of poly(acrylonitrile‐itaconic acid) precursor fibers in wet‐spinning

The skin‐core structure of poly(acrylonitrile‐itaconic acid) [P(AN‐IA)] precursor fibers in wet‐spinning has been analyzed by the means of electron probe microanalyser (EPMA), scanning electron microscope (SEM), and transmission electron microscope. The numerical solution of Fick's second law equations for diffusion in the nascent fiber was obtained by using the Method of Lines. It has been found that [P(AN‐IA)] precursor fiber composed of four parts had remarkable skin‐core structure. The sheet‐like skin, which was compact and homogeneous, had high crystallization and highly oriented structure. However, the core with low crystallization and some voids was loose, somewhat disorderly and unsystematic. Moreover, the precursor fiber had a pillar‐like layered structure along the fiber axis. The average thickness of each layer increased gradually from the skin to the endothecium. Meanwhile, a structural model of PAN precursor fiber has been built. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008