PAN原丝成形过程中孔隙结构的形成和演变

采用干湿法纺丝在梯级凝固成形条件和后续工艺下得到聚丙烯腈(PAN)原丝,利用扫描电镜、氮气吸附等方法测试研究了PAN原丝中孔隙的形成和演变。结果表明:在凝固成形阶段,PAN原丝内孔隙的形成是溶剂和非溶剂双扩散及PAN相分离双重作用的结果;PAN原丝经过沸水拉伸、干燥致密化、饱和蒸汽拉伸和热定型等处理,其纤维密度、结晶度增大,力学性能提高,其孔隙平均孔径、孔隙体积和孔隙含量均逐渐减小;PAN原丝内闭合孔隙经过拉伸后会形成新的开放孔隙,开放孔隙在干燥致密化后闭合和消失。     

PAN原丝沸水收缩率影响因素的探讨

采用溶液聚合和湿法纺丝制备碳纤维用聚丙烯腈(PAN)原丝,探讨了共聚组成、凝固浴温度、凝固浴浓度、拉伸介质和热定型温度对PAN纤维沸水收缩率的影响。结果表明,采用二元共聚物丙烯腈/甲叉丁二酸的质量比为99/1,凝固浴温度为30℃、凝固剂中二甲基亚砜质量分数为70%,热定型温度为160℃,拉伸介质为加压饱和蒸汽时,制备的PAN原丝沸水收缩率最低。     

成形条件对PAN原丝微孔结构及热性能的影响

将不同浓度的聚丙烯腈(PAN)原液在不同凝固浴温度下进行湿法纺丝,制得PAN原丝,再将PAN原丝在沸水浴中进行5倍拉伸。探讨了成形条件以及拉伸对PAN原丝微孔结构及热性能的影响。结果表明:当PAN纺丝原液质量分数为22%,凝固浴温度为10℃时,可以得到结构均匀致密的PAN原丝。PAN原丝经5倍拉伸后热分解温度降低,残留量减小。     

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基碳纤维原丝产品均质性研究

从纺丝生产工艺方面对聚丙烯腈(PAN)原丝产品均质化的影响因素进行了试验探讨。研究表明:优质的PAN原丝是碳纤维发展的基础,而均质化差的PAN原丝将导致原丝产品质量的性能缺陷及生产波动,极大的影响原丝的加工性能。     

水洗方法对PAN原丝及其碳纤维结构与性能的影响

在聚丙烯腈(PAN)基碳纤维生产中,分别采用浸涌式水洗、拍打式水洗、超声式水洗3种方法对PAN原丝进行水洗,讨论了PAN原丝的线密度对水洗效果的影响,以及3种水洗方法对PAN原丝及其碳纤维的结构与性能的影响。结果表明:在水洗流量1 m3/h、水洗温度60℃、水洗时间1.2 min的条件下,随着PAN原丝线密度的增加,原丝中二甲基亚砜(DMSO)残留量增加,浸涌式水洗受原丝线密度的影响较大,超声式水洗受原丝线密度的影响较小;在PAN原丝线密度为4.0 dtex时,PAN原丝经浸涌式、拍打式、超声式水洗后,DMSO残留量分别为1 000,200,90μg/g,相应碳纤维强度分别为5 139,5 120,4 930 MPa;浸涌式水洗对PAN纤维的损伤较小,超声式水洗对PAN纤维的损伤较大。     

聚丙烯腈碳纤维原丝改性的研究进展

从聚丙烯腈(PAN)基碳纤维的原丝改性入手,着重综述了PAN基碳纤维原丝改性的国内外现状,原丝改性主要以化学改性与物理改性为主,化学改性作为一种较为成熟的改性手段,其大大提高了碳纤维的力学性能;而物理改性主要以辐射改性为主,辐射改性能够改善预氧化过程,对碳纤维最终性能的影响尚需进一步深入研究。最后对PAN基碳纤维原丝的改性研究进行了展望。     

PAN原丝直径对碳纤维收率的影响

对不同预氧化条件下两种直径PAN原丝的碳纤维收率进行了分析,并利用TG、XPS、NMR、Raman等测试表征方法,深入讨论了原丝直径对其碳纤维收率的影响。结果表明:预氧化温度越高,PAN原丝的碳纤维收率越高,相同工艺条件下粗直径PAN原丝的碳纤维收率高于细直径原丝的碳纤维收率,粗直径PAN原丝的热失重一直低于细直径原丝的热失重,细直径PAN预氧丝的预氧化程度高于粗直径PAN原丝的预氧化程度,而不同直径预氧丝表面元素及碳纤维表面微晶结构无差异。     

拉丝工艺中张力对直接纱原丝筒外形的影响

阐述了张力对直接纱原丝筒外形影响的力学原理,通过试验验证了张力对直接纱马鞍形、高度和外径影响的规律。在相同拉丝条件下,拉丝张力越大,直接纱的马鞍形越严重;随着拉丝张力的不断增大,直接纱卷径逐渐减小,高度略微增加。     

AMPS氨化对四元聚丙烯腈原丝结构和性能的影响

利用氨水对2-丙烯酰胺-2-甲基丙磺酸(AMPS)的磺酸基进行氨化改性以制备氨化AMPS,采用丙烯腈、丙烯酸甲酯、衣康酸和氨化AMPS为聚合单体,以偶氮二异丁腈为引发剂,在溶剂二甲基亚砜中经溶液共聚合成了四元聚丙烯腈(PAN)纺丝液,并通过湿法纺丝纺制了碳纤维前驱体四元PAN原丝,分析了AMPS的氨化率对原丝结构和性能的影响。结果表明,AMPS氨化改性后成功将亲水基团NH_4~+引入到四元PAN原丝中;AMPS氨化率为0%～40%时,随着氨化率的增加,纺丝液中共聚物的接触角逐渐减小,原丝的孔隙率先下降后上升,拉伸性能先增大后减小;AMPS氨化率为30%时,原丝的孔隙率最小、拉伸性能最好、截面形貌近似为圆形,其热反应起始温度有所降低、放热峰变宽,最终制得的原丝孔隙率为12.3%,拉伸强度、拉伸弹性模量和断裂伸长率分别为7.5,123.2c N/dtex和15.2%,由此制备的碳纤维拉伸强度、拉伸弹性模量和断裂伸长率达到了4 321MPa,211GPa和2.9%,分别较未氨化时提高了12.4%,6.6%和7.4%。     

熔纺聚丙烯腈纤维的拉伸及热定型工艺

研究了熔纺聚丙烯腈 (MPPAN )纤维的拉伸及热定型工艺 ,并应用 X光衍射、取向、应力 -应变等方法对拉伸丝及定型丝的结晶性能、机械性能和沸水收缩性进行了表征 ,结果表明 :两种 MPPA N纤维都可以进行热水拉伸 ,但需严格控制拉伸温度 ;纤维拉伸以后 ,结晶度和机械性能均得到提高 ;其中AN含量为 81.6 %的 MPPAN拉伸丝可在 14 0℃以下 (以 130℃为佳 )干热定型 ,定型丝的性能和定型方式有关。     

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。     

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.     

Comparative investigation on the thermal degradation and stabilization of carbon fiber precursors

Thermal degradation and stabilization of two kinds of polyacrylonitrile (PAN) fibers have been investigated by a combination of FT-IR, differential scanning calorimetry (DSC), modulated DSC, thermogravimetry (TG), thermal shrinkage behavior, in situ mass spectrometry (MS), and tensile property examinations. The two types of precursor fibers exhibit distinct properties after oxidative stabilization, but they can both make carbon fibers with equivalent mechanical properties. Compared with PAN/itaconic acid precursor fibers, the fibers containing acrylamide comonomers show a doublet appearance, broader exothermic peak, lower threshold degradation temperature, and more amount of heat evolved in DSC thermogram, which is favorable to obtain uniform microstructures in oxidative stabilization process. The two types of samples produce different ring structures in the thermal degradation and stabilization process, as evidenced by results from tensile test, TG–MS and thermal shrinkage behavior analyses. In addition, the molecular rearrangement or melting of ordered structures accompanying with nitrile polymerization was also detected from modulated DSC.     

The index of dry‐jet wet spinning for polyacrylonitrile precursor fibers

A new spinning index for a PAN precursor fiber is proposed that includes the viscosity of a spinning dope, the thermodynamic affinity, and the draw ratio during the spinning process. Through dry‐jet wet spinning, six types of PAN precursor fibers with different spinning parameters, including solid content, solvent content in a bath, and draw ratio, were fabricated and analyzed with tensile tests, SEM, and XRD. The results show that the spinning index can reflect the mechanical properties of the fibers but is less indicative of crystallinity. Hence, the current spinning index is recommended for use as an indicator for the mechanical properties of PAN precursor fibers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41265.     

Influence of γ‐ray irradiation on structure and properties of PAN precursor fibers

To improve the oxidative efficiency of polyacrylonitrile (PAN) precursors, modification of PAN precursors was employed by gamma ray irradiation. Effects of irradiation on the structure and properties of PAN precursors were investigated. The results showed that cyclized structure in the precursors was formed after γ‐ray irradiation. Meanwhile, irradiation could reduce the heat evolved, relax the exothermic behavior, decrease the mechanical properties and enhance the density of PAN fibers. It is supposed that the modification of γ‐ray irradiation could remarkably accelerate the stabilization process of PAN precursors and reduce the production cost of resulting carbon fibers. POLYM. ENG. SCI., 56:1313–1318, 2016. © 2016 Society of Plastics Engineers     

KMnO4对改性聚丙烯腈纤维物理与化学结构的影响

通过X射线衍射、傅里叶变换红外光谱、扫描电子显微镜和拉伸仪研究了KMnO_4对改性聚丙烯腈(PAN)纤维化学结构、物理结构和力学性能的影响。实验结果表明,在KMnO_4改性PAN纤维过程中使PAN纤维不仅发生了氰基环化反应,还伴随氰基的水解;随改性温度的升高PAN纤维晶粒尺寸与结晶度呈现下降趋势;同时改性PAN纤维的断裂伸长率逐渐升高、杨氏模量与拉伸强度逐渐降低。     

Effects of heat treatment on tensile properties of diacetate fibers

Diacetate filaments were heat‐treated (without tension or with tension) under dry‐heat or wet‐heat environment, respectively. The effects of temperature, time, and tension on tensile properties of diacetate fibers after heat treatments were discussed. The results show that diacetate fibers present no obvious improvement on its tensile properties after dry‐heat treatments without tension. It was also found that during dry heat treatments with tension, the increase in tensile properties of fibers mainly depends on temperature and tension. Moreover, being dry‐heat treated with tension instant after wet‐heat treatment without tension, diacetate fibers exhibit a higher improvement on its tensile properties comparing with dry heat method with tension. The shrinking measurement for the fibers indicates different supermolecular structures were developed in the fiber before treatment and after treatment, which leads to the different extent in the improvement of tensile properties for the fibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101:787–791, 2006     

Structural changes during the thermal stabilization of modified and original polyacrylonitrile precursors

A polyacrylonitrile (PAN) precursor fiber of a special grade for preparing carbon fibers was modified by the impregnation of an aqueous KMnO₄ solution. The effects of the modification on the lateral and morphology structure, related to the crystalline properties of both the precursors and preoxidized fibers, such as the orientation index, crystal size, and crystallinity index, were measured by wide‐angle X‐ray diffraction. For both modified and original PAN fibers, a comparative study of the changes of the elemental content during the process of preoxidation, the relations between the thermal stress and heat‐treatment temperature, and the effect of the modification on the skin/core structure of a preoxidized fiber were also introduced by the use of elemental analysis, optical microscopy, and so on. The modification of KMnO₄ was demonstrated to increase the density, increase the crystallinity index, increase the preferred orientation index, and decrease the crystal size for a modified precursor fiber and for a preoxidized fiber developed from a modified precursor fiber after a different heat‐treatment temperature. KMnO₄ also showed a catalytic action, accelerating the rate of preoxidation and reducing the time of thermal stabilization; this improved the homogenization of the cross‐section structure and led to an improvement in the tensile strength of 15–20% and an improvement in the elongation of 20–30% in the resulting carbon fibers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2047–2053, 2005