针对二元共聚聚丙烯腈(PAN)纤维的热应力和聚集态结构特点,借用差示扫描量热(DSC)分析、广角X射线衍射(WAXD)、红外光谱(FTIR)等表征手段研究了预处理阶段(180℃)纤维热应力变化与最终碳纤维结构及性能的关联性.实验结果表明:对于取向度较高,但热应力较大的二元共聚PAN纤维,在180℃进行适当的应力松弛处理有利于最终碳纤维力学性能的提高.进一步的分析表明,随着预处理阶段纤维热应力的降低,PAN纤维内部准晶区的取向度逐渐下降,而纤维的环化反应活化能明显降低,相对环化率逐渐增大,相应碳纤维中类石墨晶体的层间距呈现先减小后增大的趋势,类石墨晶体的堆叠厚度则是先增大后减小;与之对应的碳纤维的拉伸强度以及拉伸模量也呈现出先增大后减小的趋势.综合研究结果表明:对二元共聚PAN纤维进行适当的热应力松弛处理可有效改善最终的碳纤维结构参数,提高其力学性能.
参考文献
[1] | Frank E,Hermanutz F,Buchmeiser M R.Carbon fibers:precursors,manufacturing,and properties[J].Macromolecular Materials and Engineering,2012,297(6):493-501. |
[2] | Mathur R B,Dhami T L,Bahl O P.Shrinkage behaviour of modified PAN precursors-its influence on the properties of resulting carbon fibre[J].Polymer Degradation and Stability,1986,14(2):179-187. |
[3] | Bahl O P,Manocha L M.Shrinkage behaviour of polyacrylonitrile during thermal treatment[J].Die Angewandte Makromolekulare Chemic,1975,48(1):145-159. |
[4] | 刘杰,王雷,张旺玺,等.热稳定化过程中PAN纤维热应力与热化学反应的关联性[J].新型炭材料,2005,20(4):343-349.Liu Jie,Wang Lei,Zhang Wangxi,et al.Relationships tween thermal stress and the thermal-chemical reaction of PAN fibers during thermal stabilization[J].New Carbon Materials,2005,20(4):343-349. |
[5] | Qin X,Lu Y,Xiao H,et al.Improving preferred orientation and mechanical properties of PAN-based carbon fibers by pretreating precursor fibers in nitrogen[J].Carbon,2011,49(13):4598-4600. |
[6] | 刘杰,李仍元,王平华,等.碳化过程中PAN基碳纤维结构与力学性能变化的研究[J].复合材料学报,1993,10(3):75-82.Liu Jie,Li Rengyuan,Wang Pinghua,et al.Progression of morphological structure and mechanical properties of PAN oxidized fiber in carbonization stage[J].Acta Materiae Compositae Sinica,1993,10(3):75-82. |
[7] | Lian F,Liu J,Ma Z,et al.Stretching-induced deformation of polyacrylonitrile chains both in quasicrystals and in amorphous regions during the in situ thermal modification of fibers prior to oxidative stabilization[J].Carbon,2012,50(2):488-499. |
[8] | Bahl O P,Mathur R B.Effect of load on the mechanical properties of carbon fibres from pan precursor[J].Fibre Science and Technology,1979,12(1):31-39. |
[9] | Blaine R L,Kissinger H E.Homer Kissinger and the Kissinger equation[J].Thermochimica Acta,2012,540:1-6. |
[10] | Wang Z X.Evolution of structure and properties of PAN precursors during their conversion to carbon fibers[J].Carbon,2003,41(14):2805-2812. |
[11] | Liu J,Lian F,Ma Z K,et al.Effects of deformation-induced orientation on cyclization and oxidation of polyacrylonitrile fibers during stabilization process[J].Chinese Journal of Polymer Science,2012,30(6):786-795. |
[12] | Lai C,Zhong G,Yue Z,et al.Investigation of post-spinning stretching process on morphological,structural,and mechanical properties of electrospun polyacrylonitrile copolymer nanofibers[J].Polymer,2011,52(2):519-528. |
[13] | 刘杰,白艳霞,田宇黎,等.电化学表面处理对碳纤维结构及性能的影响[J].复合材料学报,2012,29(2):16-25.Liu Jie,Bai Yanxia,Tian Yuli,et al.Effect of the process of electrochemical modification on the surface structure and properties of PAN-based carbon fibers[J].Acta Materiae Compositae Sinica,2012,29(2):16-25. |
[14] | Dalton S,Heatley F,Budd P M.Thermal stabilization of polyacrylonitrile fibres[J].Polymer,1999,40(20):5531-5543. |
[15] | Fitzer E,Müller D J.The influence of oxygen on the chemical reactions during stabilization of pan as carbon fiber precursor[J].Carbon,1975,13(1):63-69. |
[16] | Gupta A,Harrison I R.New aspects in the oxidative stabilization of PAN-based carbon fibers[J].Carbon,1996,34(11):1427-1445. |
[17] | Jain M,Balasubramanian M,Desai P,et al.Conversion of acrylonitrile-based precursors to carbon fibres[J].Journal of Materials Science,1987,22(1):301-312. |
[18] | 于美杰.聚丙烯腈纤维预氧化过程中的热行为与结构演变[D].济南:山东大学,2007.Yu Meijie.Thermal behavior and structural evolution during oxidative atabilization of polyacrylonitrile fibers[D].Jinan:Shandong University,2007. |
[19] | Matta V K,Mathur R B,Bahl O P,et al.Crystallinity of PAN precursors[J].Carbon,1990,28(1):241-243. |
[20] | Xue Y,Liu J,Liang J.Correlative study of critical reactions in polyacrylonitrile based carbon fiber precursors during thermal-oxidative stabilization[J].Polymer Degradation and Stability,2013,98(1):219-229. |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分:
-
10%
-
20%
-
30%
-
40%
-
50%