聚丙烯腈热稳定化纤维的裂解行为

doi:10.11868/j.issn.1001-4381.2015.001283

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摘要

在聚丙烯腈基碳纤维（PANCF）制备过程中会有40%~50%的质量损失，主要发生在300~800℃范围内。对PAN裂解失重行为的研究有利于理解PANCF类石墨结构的形成机理，为制备高性能碳纤维和提高碳化收率提供理论依据。通过热重分析法（TGA）模拟PAN纤维的裂解失重过程，结果表明：在空气中进行稳定化的纤维主要有两个阶段的裂解，分别受腈基的环化率和氧含量控制。环化率和氧含量通过影响裂解行为在碳纤维中形成的缺陷结构，最终影响碳纤维的致密性。环化率越高，形成的缺陷结构越少，碳纤维的致密性越好；相反氧含量越高，形成缺陷结构越多，碳纤维的致密性越差。

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	雷帅
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	徐樑华

关键词 ：聚丙烯腈, 稳定化, 裂解, 碳纤维, 体密度

Abstract：

In the temperature range of 300-800℃, 40%-50% of the mass lost during the processing of polyacrylonitrile based carbon fiber (PANCF). Understanding the degradation behavior will be valuable in understanding the formation mechanism of pseudo-graphite structure, and providing theoretic basis for producing high performance carbon fiber and increasing the carbonization yield. The simulation of the degradation progress was carried out on the thermogravimetric analyzer (TGA), the results show that there are two degradation steps for PAN fiber stabilized in air, and controlled by cyclization coefficient and oxygen content. The cyclization coefficient and oxygen content are effective to the density of carbon fiber by influencing the degradation behavior, which cause defects in the fiber. The higher cyclization coefficient leads to form less structural defects and higher density of the fiber; on the contrary, the higher oxygen content leads to form more structural defects and lower density of the fiber.

Key words： polyacrylonitrile stabilization degradation carbon fiber bulk density

收稿日期: 2015-10-26 出版日期: 2017-05-17

中图分类号:

TQ342.31

基金资助:国家科技支撑计划(2014BAE07B00)

通讯作者: 徐樑华 E-mail: xulh@mail.buct.edu.cn

作者简介: 徐樑华(1960-), 男, 研究员, 主要从事高性能聚丙烯腈基碳纤维的研究, 联系地址:北京市朝阳区北三环东路15号北京化工大学碳纤维及复合材料研究所(100029), E-mail:xulh@mail.buct.edu.cn

引用本文:

雷帅, 张校, 钟珊, 刘正博, 曹维宇, 徐樑华. 聚丙烯腈热稳定化纤维的裂解行为[J]. 材料工程, 2017, 45(5): 59-63.
Shuai LEI, Xiao ZHANG, Shan ZHONG, Zheng-bo LIU, Wei-yu CAO, Liang-hua XU. Degradation Behavior of Thermal Stabilized Polyacrylonitrile Fibers. Journal of Materials Engineering, 2017, 45(5): 59-63.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2015.001283 或 http://jme.biam.ac.cn/CN/Y2017/V45/I5/59

Fig.1 共聚PAN原丝和空气中稳定化纤维的红外光谱

Fig.2 PAN原丝(a)和空气中稳定化的纤维(b)在N₂中从室温至1000℃的TG和DTG曲线

Fig.3 具有不同环化率的PAN稳定化纤维的红外光谱

Fig.4 不同环化率(a)和氧含量(b)的PAN稳定化纤维在氮气中从室温至1000℃的TG和DTG曲线

Fig.5 稳定化纤维的氧含量(a)和环化率(b)对其高温裂解后拉曼光谱D峰的半高宽的影响

Table 1 稳定化纤维的氧含量w(O)和环化率η与碳纤维体密度ρ_v的关系

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