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。     

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。     

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.     

浅析聚丙烯腈基碳纤维焦油形成的原因

根据聚丙烯腈基碳纤维生产工艺路线,从原丝、预氧化、碳化工艺及结构上分析了聚丙烯腈基碳纤维焦油形成的原因。其主要原因为碳化前纤维缺陷结构的遗传、碳化中分子键的热断裂和分子链的无规热裂解。     

聚丙烯腈纤维预氧化过程——Ⅰ.皮芯二重结构的研究

<正> 聚丙烯腈纤维的预氧化过程是制备高强高模量碳纤维的重要环节,预氧化过程的研究对改进制备碳纤维的工艺,提高碳纤维的性能以及纺制新型原丝等等都有密切的关系,因此在这方面仍然进行着大量工作。近年来为了缩短预氧化时间,采用提高预氧化温度的措施,这样,聚丙烯腈纤维在某些预氧化条件下会形成皮芯二重结构,我所制备高强Ⅰ型碳纤维的预氧化纤维就是这样     

一种创新的运用电子技术制造碳纤维的方法

重点介绍了运用电子技术制造碳纤维的创新思路和实践,具体阐述了PAN原丝射频负压软等离子预氧化,预氧化纤维微波法碳化和碳纤维射频法石墨化工艺过程的设备、原理和工艺流程。     

PAN/PPG纤维预氧化及碳纤维结构和性能研究

采用聚丙二醇(PPG)与聚丙烯腈(PAN)共混制备的PAN/PPG原丝进行预氧化和碳化,利用SEM、FTIR、元素分析仪、力学性能测试等仪器和手段,研究了PPG的加入对预氧丝和碳丝的结构和性能的影响.研究发现:PPG的加入使PAN预氧丝的表面结构更加均匀,减少了碳纤维中的孔洞;同时还促进了纤维在预氧化和碳化过程中的氧化...     

最新专利

正一种抑制碳纤维结构不均匀性的方法公开号CN105544021A/公开日2016-05-04/申请人上海应用技术学院题述方法具体如下:将纤维原丝在空气气氛中,经250~300℃预氧化处理后,在氮气、氩气、氦气或组合气氛任意一种气氛中,将预氧化纤维直接由微波加热法进行650~1 600℃碳化处理。所制得的微波加热碳纤维与传统外加热方式制得的碳纤维相比,在同等温度下,碳纤维的碳化程度更高,皮芯结构降低,整体结构均匀。一种聚乙烯/聚丙烯抗菌复合纤维公开号CN     

高模高强碳纤维制备技术有望国产化

<正>2015年4月10日,由北京化工大学承担的北京市科委新材料专项课题"M40J高模高强碳纤维国产化制备技术研发"通过专家验收。M40J高模高强碳纤维是支撑航天技术发展的重要结构材料。该课题突破了国产M40J级高模高强碳纤维石墨微晶叠层厚度的调控、原丝牵伸匹配和预氧化环状结构含量控制等关键技术,形成了原丝和预氧化碳化石墨化的完整制备工艺,能满足卫星结构用碳     

硝酸法聚丙烯腈纤维热性能的研究

<正> 一 前言 聚丙烯腈纤维是制造碳纤维的主要原料之一。其方法是先将原丝在300℃以下的空气中进行预氧化处理,形成稳定的梯型聚合物,然后,再在惰性气体保护下,于1000～1400℃进行碳化,形成石墨结构的碳纤维。预     

The effects of carbonization temperature on the properties and structure of PAN‐based activated carbon hollow fiber

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate and then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of carbonization temperature of PAN hollow fiber precursor on the microstructure, specific surface, pore‐size distribution, and adsorption properties of PAN‐based carbon hollow fiber (PAN‐CHF) and PAN‐based activated carbon hollow fibers (PAN‐ACHF) were studied in this work. After the activation process, the surface area of the PAN‐ACHF increased very remarkably, reaching 900 m² g^?1 when carbonization is 1000°C, and the adsorption ratios to creatinine and VB₁₂ of ACHF were much higher than those of CHF, especially to VB₁₂. The different adsorption ratios to two adsorbates including creatinine and VB₁₂ reflect the number of micropores and mesopores in PAN‐ACHF. The dominant pore sizes of mesopores in PAN‐ACHF are from 2 to 5 nm. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2155–2160, 2005     

国内外PAN基碳纤维的研究进展

介绍了聚丙烯腈基碳纤维材料的应用与聚丙烯腈基碳纤维生产技术在国内外的现状与发展,重点介绍了PAN基碳纤维原丝的制备工艺,聚合体系的组成与研制,纺丝工艺的特点及PAN原丝预氧化工艺和PAN的碳化工艺的研究。在现阶段我国聚丙烯腈基碳纤维在生产与研制上与国外的差距,并对高性能碳纤维复合材料产业在我国的发展作了展望。     

The effect of the side chain of acrylate comonomers on the orientation,pore-size distribution,and properties of polyacrylonitrile precursor and resulting carbon fiber

The side-chain size of acrylate comonomer in polyacrylonitrile (PAN) precursor markedly influences the microstructure of PAN fiber and its resulting carbon fiber. In this paper, we propose that the model of the crystal orientation of PAN precursor and its resulting carbon fiber can explain the effect of the side-chain size of acrylate comonomer on the orientation of PAN fiber and carbon fiber. When PAN precursor contains a larger side chain of comonomer, PAN precursor has the preferred crystal orientation and higher crystallinity and the orientation of its resulting carbon fiber unexpectedly decreases. This is because the larger the side chain is, the lower is the orientation of the amorphous region of PAN fiber; as a result, the average orientation after carbonization decreases. In the same mole fraction of comonomer, the carbon fiber based on PAN precursor with a smaller side chain of acrylate comonomer has better mechanical properties and higher yield.     

Effects of the oxidation temperature on the structure and properties of polyacrylonitrile‐based activated carbon hollow fiber

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate, oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of the oxidation temperature of the PAN hollow fiber precursor on the microstructure, specific surface, pore size distribution, and adsorption properties of PAN‐based activated carbon hollow fiber (PAN‐ACHF) were studied. When PAN hollow fibers were oxidized at 270°C, because of drastic oxidation, chain scission occurred, and the number of pores within and on the surface of the resultant PAN‐ACHF increased, but the pores were just in the thinner region of the skin of PAN‐ACHF. The surface area of PAN‐ACHF reached a maximum when the oxidation temperature was 270°C. The adsorption ratios to creatinine were all higher than 90% at all oxidation temperatures, and the adsorption ratio to VB₁₂ reached a maximum (97%) at 230°C. The dominant pore sizes of the mesopores in PAN‐ACHF ranged from 2 to 5 nm. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 203–207, 2005     

Effects of oxidation time on the structure and properties of polyacrylonitrile‐based activated carbon hollow fiber

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate, then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of oxidation time of PAN hollow fiber precursor on the microstructure, specific surface, pore size distribution, and adsorption properties of PAN‐based activated carbon hollow fiber (PAN‐ACHF) were studied in this work. Both of specific surface area and adsorption ratio to VB₁₂ reach maximums when PAN hollow fibers are oxidized for 5 h in air. The adsorption ratios for creatinine are all higher than 90% over all oxidation time. After 5 h of oxidation, the number of pores on the surface obviously increases, and the pore size is uniform. After 7 h of oxidation, the number of macropores in PAN‐ACHF increases. The dominant pore sizes of mesopores in PAN‐ACHF range from 2 to 5 nm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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.     

聚丙烯腈预氧化纤维组织结构的遗传与演变研究

采用扫描电镜(SEM)和透射电镜(TEM)仪器和方法,对聚丙烯腈(PAN)原丝和不同温度阶段预氧丝的表面形貌、断面形貌和内部组织结构进行了系统的分析。结果表明,PAN原丝的原纤结构在整个预氧化过程中是具有遗传性的,随着预氧化的不断进行,原纤的韧性逐渐降低,原纤之间的结合更为紧密;预氧化反应由纤维外部向芯部逐步进行,形成了组织致密、脆性高的皮层和组织疏松、韧性高的芯部。皮层区域的晶粒尺寸细小,分布均匀,无择优取向,非晶组织较为致密;而芯部区域的组织粗大,呈现出沿纤维轴向排列的层片状结构,越靠近芯部,层片的取向越明显。     

PAN基碳纤维硬脆现象原因分析

在PAN基高强碳纤维生产制备过程中有时会出现碳纤维硬脆现象,碳纤维的硬脆会严重影响到碳纤维的强度,通过对纤维结构和生产工艺的分析取证,从皮芯结构、并丝现象、低温段废气排放、表面缺陷和石墨化度五个方面阐述了碳纤维硬脆现象出现的原因,并提出了相应的解决办法。     

Effects of activation temperature on the properties and structure of PAN‐based activated carbon hollow fiber

Polyacrylonitrile (PAN) hollow fibers were pretreated with ammonium dibasic phosphate, then further oxidized in air, carbonized in nitrogen, and activated with carbon dioxide. The effects of activation temperature of a precursor fiber on the microstructure, specific surface, pore‐size distribution, and adsorption properties of PAN‐based activated carbon hollow fibers (PAN‐ACHF) were studied in this work. After the activation process, the BET surface area of the PAN‐ACHF and surface area of mesopores in the PAN‐ACHF increased very remarkably and reached 1422 m² g^?1 and 1234 m² g^?1, respectively, when activation temperature is 1000°C. The adsorptions to creatinine and VB₁₂ of PAN‐ACHF were much high and reached 99 and 84% respectively. In PAN‐ACHF which went through the activation at 700°C and 800°C, the micropore filling mainly occurred at low relative pressures, multimolecular layer adsorption occurred with the increasing of relative pressure, and the filling and emptying of the mesopores by capillary condensation occurred at high relative pressures. But in PAN‐ACHF which went through the activation at 900°C, a mass of mesopores resulted in the large pore filling by capillary condensation. The dominant pore sizes of mesopores in PAN‐ACHF are from 2 nm to 5 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3778–3783, 2006