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。     

金属离子对聚丙烯腈纤维预氧化过程的影响

采用浸渍的方法将不同种类金属离子Na、Ca、Fe引入聚丙烯腈(PAN)纤维,并将PAN纤维在空气中进行预氧化处理。借助于原子吸收光谱(AAS)、元素分析(EA)研究了PAN预氧化纤维的组成;通过X射线衍射(XRD)、傅立叶变换红外光谱(FTIR)、差示扫描量热分析(DSC)、热失重(TG)等多种表征手段,研究了PAN预氧化纤维的结晶结构、化学反应及热性能,从而研究了金属离子对聚丙烯腈纤维预氧化过程的影响。从多种表征手段的研究结果表明,金属离子影响了PAN纤维预氧化进程,具体表现为添加金属离子后,PAN预氧化纤维组成改变,密度降低,代表分子环化反应所产生的六元环特征衍射峰增长缓慢,代表原丝结晶结构的特征衍射峰消失迟缓,代表环构化的官能团较少,含有金属离子的PAN预氧化纤维由于预氧化不足导致在氮气气氛下放热量增加,热失重增加。     

磷酸二氢铵对聚丙烯腈纤维预氧化程度及热稳定性的影响

聚丙烯腈(PAN)纤维的预氧化过程是PAN基炭纤维生产中最耗能耗时的阶段。为了加快PAN纤维的预氧化过程,提高PAN纤维的预氧化程度,采用非金属化合物磷酸二氢铵(NH_4H_2PO_4)对PAN纤维进行改性,探讨了磷酸二氢铵对PAN纤维化学结构和热性能的影响。通过傅里叶红外光谱(FT-IR)和X射线衍射(XRD)分析得到,PAN纤维的预氧化程度随着预氧化温度和试验设定的NH_4H_2PO_4浓度范围内升高而升高。与未改性PAN纤维相比,相同温度下,改性PAN纤维环化度更高,在180℃和200℃低温条件下更为明显,240℃及260℃的促进效果一般,另外改性PAN纤维在240℃可提前完成环化反应。热重(TGA)结果表明,NH4H2PO4受热分解产生的磷酸与羟基反应导致分子链交联,能降低预氧化过程中的热失重,提高热稳定性。     

臭氧气氛中聚丙烯腈纤维预氧化过程中的热行为

通过测量聚丙烯腈(PAN)纤维在空气和臭氧气氛下预氧化过程中的热应力行为,比较空气和臭氧气氛中预氧化所得纤维的物化性质。结果表明:PAN纤维在臭氧气氛中进行预氧化时,纤维的物理收缩应力和化学收缩应力比空气中的小,应力松弛严重;纤维在臭氧气氛中的敏感温度均比空气中的高,化学反应推迟;相同的升温速率下,臭氧气氛中纤维发生化学反应的时间较空气中的少,臭氧中纤维的化学反应速率较空气中的快;两种气氛中纤维的体积密度相差很小,臭氧中纤维皮芯结构状况较严重。     

Fe~(3+)对聚丙烯腈纤维预氧化反应的影响

在空气气氛中对含有Fe3+的聚丙烯腈(PAN)纤维进行预氧化处理,研究了Fe3+对PAN纤维氰基环构化和纤维结构的影响及其影响机理。结果表明:在相同的预氧化条件下,含有Fe3+的PAN纤维的预氧化程度较低,添加Fe3+后,减缓了PAN纤维预氧化进程;含有Fe的PAN预氧化纤维的体密度较低,氮气气氛下,热失重增加;在PAN纤维预氧化时,纤维表面的Fe元素大部分以Fe3O4的形式包覆在纤维表面,阻碍氧的扩散,延缓PAN纤维预氧化进程。     

PAN预氧化纤维结构与热处理温度的关系

在空气气氛中不同温度下对聚丙烯腈(PAN)原丝热处理8 h,制得PAN预氧化纤维。借助差示扫描量热分析、红外吸收光谱、X射线衍射、固体核磁等测试手段,表征了不同温度处理的PAN纤维的预氧化程度,研究了PAN预氧化纤维的结构特点。结果表明:不同温度下PAN纤维的预氧化程度不同,随着温度的提高而提高;PAN纤维预氧化程度不同,缘于不同温度下预氧化反应差异造成的预氧化结构的不同;预氧化温度越高,未环化的C≡N结构中共轭的C≡N结构相对含量越多,不利于进一步环化;环化反应在190~220℃较剧烈,在220℃以后反应趋于缓和;脱氢反应在190~210℃比较缓慢,在温度高于220℃开始剧烈进行;190℃以上发生氧化反应。     

预氧化温度对静电纺Co/C复合纳米纤维形貌与结构的影响

通过调节静电纺丝过程环境因素制备了CoAc_2/PAN前驱体纤维,再经过热处理得到Co/C复合纳米纤维,分析了预氧化温度对纤维形貌与结构的影响。研究结果表明:当预氧化温度为160℃时,纤维中的PAN未形成稳定的耐热梯形结构,在碳化时纤维扭曲,生成枝节状物质;当预氧化温度为230℃时,碳化后可得到表面光滑、均匀,结构完好的Co/C复合纳米纤维;当预氧化温度为300℃时,纤维中的聚合物大分子遭到破坏,导致后续的碳化结晶过程无法正常进行,纤维形成颗粒聚集态。     

臭氧预氧化聚丙烯腈纤维工艺条件的研究

通过在线监测聚丙烯腈纤维的热收缩行为,对臭氧预氧化工艺条件进行了研究。实验结果表明:超过150℃通入臭氧会引起纤维分子链断裂,对预氧化不利;低温下恒温,臭氧预氧化效果不明显;恒温温度过高,加快了臭氧的分解,臭氧预氧化的效果也不明显,因此最佳的恒温温度应为125℃。同时对恒温时间进行了优化,发现当恒温时间达到1h,臭氧会引起晶区PAN纤维分子链的断裂,对预氧化不利,因此最佳恒温时间应为0.5h。     

基于低环化反应活化能的PAN纤维快速预氧化研究

本文研究了PAN纤维环化反应活化能与其耐热性的关联性,进而开展了快速预氧化的研究。研究结果表明:通过聚合第二单体对聚合物结构的改性,可以实现对纤维环化反应活化能的有效调控,环化反应活化能越低,PAN纤维的耐热性就越高,在预氧化过程中能够承受较高的预氧化温度; PAN纤维的环化反应和氧化反应具有不同步性,且在230℃之前二者均没有显著发生。基于此,本文通过对PAN纤维的低环化反应活化能和高预氧化温度的综合控制,预氧化时间大幅缩短至35 min以内,所制备的碳纤维(T700级)的拉伸强度为5 411 MPa,CV值为3. 9%。     

硼酸改性PAN热稳定化行为的研究

将硼酸直接加入聚丙烯腈(PAN)聚合液中,制成硼酸改性PAN膜,采用差示扫描量热(DSC)法、傅里叶变换红外光谱(FTIR)、元素分析等手段分析了硼酸对PAN热稳定化过程的影响。结果表明:硼酸改性提高了PAN的热稳定化反应活化能,并使放热峰值温度提高,当硼酸质量分数为2%时,活化能达271.27kJ/mol;硼酸含量越高,对环化反应的抑制作用越强,相对环化率越低;经过相同时间预氧化,改性PAN氧含量相对较低,硼酸改性阻碍了致密氧化层的快速形成,有利于减轻皮芯结构。     

Correlation of chemical shrinkage of polyacrylonitrile fibres with kinetics of cyclization

It has been established that the most important step in the production of carbon fibres from polyacrylonitrile (PAN) precursor fibres is the oxidative thermal treatment applied. During this treatment, physical phenomena and chemical reactions take place accompanied by the shrinkage of the fibres, which has a physical or chemical origin, depending on the nitrile cyclization reactions. The aim of the present study is to establish a correlation between the chemical shrinkage of PAN fibres and the kinetics of cyclization reactions. Based on the isothermal treatment of PAN fibres, we developed a method in order to distinguish between physical and chemical shrinkages. The onset time for the chemical shrinkage follows a relationship with temperature. Chemical shrinkage versus cyclization time data were fitted with the exponential rise to the maximum of the curves. Furthermore, the cyclization kinetics was studied using differential scanning calorimetry and the kinetic parameters determined were identical to those calculated from the chemical shrinkage, demonstrating that the latter is directly related to the kinetics of the cyclization reactions. It was therefore concluded that according to the method developed to distinguish the physical from the chemical shrinkages: (1) there exists a certain onset time for a given treatment temperature to trigger the chemical shrinkage; (2) cyclization reactions do not start below a limiting temperature of 168 °C; (3) at 340 °C, the temperature where the cyclization reactions are completed, the maximum shrinkage is 24%; and (4) the oxidized PAN fibres contain mainly ladder polymer structures with approximately symmetrical sequences connected in angled positions. Copyright © 2007 Society of Chemical Industry     

Carbothermal synthesis of boron nitride coating on PAN carbon fiber

Boron nitride (BN) thin coating has been formed on the surface of chemically activated polyacrylonitrile (PAN) carbon fiber by dip coating method. Dip coating was carried out in saturated boric acid solution followed by nitridation at a temperature of 1200 °C in nitrogen at atmospheric pressure to produce BN coating. Chemical activation improved surface area of PAN fiber which favours in situ carbothermal reduction of boric acid. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) have shown the formation of boron nitride. The X-ray photoelectron spectroscopy reveals that the coating forms a composite layer of carbon, BN/BO_xN_y and some graphite like BCN with local structure of B–N–C and B(N–C)₃. The oxidation resistance of the coated fiber was significantly higher than uncoated carbon fiber. Tensile strength measurement reveals that the BN coated fiber maintained 90% of its original strength. As compared to chemical vapor deposition (CVD), this process is simple, non-hazardous and is expected to be cost effective.     

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。     

The reaction of boric acid with wood in a polystyrene matrix

The reaction of boric acid with wood fibers in a polymer melt was examined using ¹³C-nuclear magnetic resonance (NMR), ¹¹B-NMR, differential scanning calorimetry, dynamic mechanical analysis, and component extraction and by the determination of material properties. Samples were blended at 350and 380°F in a roll mill. The use of a plasticizer in the melt to facilitate the reaction of the acid with the wood fiber was studied. NMR data showed that no significant reaction occurred between the boric acid and the polystyrene. Experimental evidence supports the reaction of boric acid with wood components. The ultimate strength of the composites was either reduced or not significantly altered by the reaction, depending upon conditions. However, the stiffness increased significantly with boric acid additions for the 350°F reactions, but behaved differently for the same additions at 380°F. The glass transition temperature of the polystyrene was lowered by the addition of plasticizer, as expected, while boric acid addition had little effect. Extracted samples showed that some boric acid remained with the wood fraction. These preliminary data suggest that boric acid does react with wood fiber under the conditions of this study. These investigations illustrate the feasibility of performing chemical reactions on the wood phase of wood/polymer composites during the extrusion process. Further research is recommended. © 1996 John Wiley & Sons, Inc.     

Oxidative stabilization of PAN/SWNT composite fiber

PAN/SWNT composite fibers have been spun with 0, 5, and 10 wt% single wall carbon nanotubes (SWNTs). Tensile fracture surfaces of polyacrylonitrile (PAN) fibers exhibited extensive fibrillation, while for PAN/SWNT composite fibers, tendency to fibrillate decreased with increasing SWNT content. The reinforcing effect of SWNTs on the oxidized polyacrylonitrile (PAN) fiber has been studied. At 10 wt% SWNTs, breaking strength, modulus, and strain to failure of the oxidized composite fiber increased by 100%, 160%, and 115%, respectively. Tensile fracture surfaces of thermally stabilized PAN and the PAN/SWNT fibers exhibited brittle behavior and well distributed SWNT ropes covered with the oxidized matrix can be observed in the tensile fracture surfaces of the fibers. No de-bonding has been observed between unoxidized or the oxidized PAN matrix and the nanotube ropes. Higher strain to failure of the oxidized composite fiber as compared to that of the oxidized control PAN fiber also suggests good adhesion/interaction between SWNT and the oxidized matrix. Thermal stresses generated on the composite fiber during the oxidation process were lower than those for the control fiber. The potential of PAN/SWNT composite fiber as the precursor material for the carbon fiber has been discussed.     

Gel-spun carbon nanotubes/polyacrylonitrile composite fibers. Part III: Effect of stabilization conditions on carbon fiber properties

The oxidative stabilization process of gel-spun carbon nanotube (CNT)/polyacrylonitrile (PAN) composite fibers have been studied and optimized. Optimum stabilization time depends on both the applied tension and temperature. Various characterization methods including thermal shrinkage, dynamic mechanical analysis, infrared spectroscopy, and wide angle X-ray diffraction are used to monitor the chemical and structural evolution during stabilization and carbonization. The relationship between the stabilization conditions of CNT/PAN composite fiber and the tensile properties of the resulting carbon fibers were investigated. By optimizing stabilization conditions, CNT/PAN based carbon fibers with a tensile strength of 4 GPa and a tensile modulus of 286 GPa were obtained using batch carbonization processing at 1100 °C.     

Shrinkage of short PP and PAN fibers under hot-stage microscope

Marked shrinkage behavior when heated is typical of semicrystalline polymer fibers such as polypropylene (PP) and polyacrylonitrile (PAN). Shrinkage of PP and PAN fibers may give the possibility to control the spalling tendency of fiber concrete under the heat exposure of fire. Cut staple fibers are normally delivered for concrete reinforcement. Modern methods for continuous fibers cannot be used by the end-user for shrinkage determination of commerical staple fiber grades. The shrinkage of five different commercial staple fibers specially designed for concrete reinforcement was studied under a hot-stage microscope. Significant differences in cumulative shrinkages of the various PP and PAN fibers were detected, shrinkages being 3–15% with PP fibers and 6–7% with PAN fibers at a temperature of 150–170°C. At about 160–165°C, PP fibers melt, whereas PAN fibers continue shrinking. Hot-stage microscopy provides a simple and a relatively accurate method for estimating thermal shrinkage of staple PP and PAN fibers, the deviations from measured average values remaining typically at 10–15%. © 1995 John Wiley & Sons, Inc.     

醋酸处理对腈纶延伸性能影响的研究

利用正交实验研究了在不同实验条件下用醋酸处理腈纶对其延伸性的影响。实验结果表明,反应温度140℃,醋酸质量分数9%,反应时间30~60min,可以得到伸长率达到50%以上的高延伸性腈纶。在正交实验的基础上,进一步进行了将反应温度提高到150℃以上的实验。结果表明,反应温度提高到150℃及以上时,纤维的强度、断裂伸长都不再提高,反而呈下降趋势,说明用醋酸提高腈纶的延伸性能,反应温度应控制在140℃左右。