Yao Zhiqiang, Xia Anqi, Wang Dongzhi, Wang Chengguo
School of Materials Science and Engineering, University of Jinan, Jinan, Shandong, 250022, People's Republic of China.
School of Materials Science and Engineering, Shandong University, Jinan, Shandong, 250061, People's Republic of China.
Nanotechnology. 2023 Oct 13;35(1). doi: 10.1088/1361-6528/acfef7.
In order to reduce the etching effect of the catalysts to carbon fibers caused by high temperature during the chemical vapor deposition (CVD) process, four multi-element catalysts, Fe-Co, Fe-Ni, Co-Ni and Fe-Co-Ni, were used to realize the low temperature growth of carbon nanotubes (CNTs) on carbon fibers at 350 °C-400 °C. The results show that the growth state of CNTs has a great relationship with the type of catalysts. The catalytic efficiency of Fe-Co catalysts is low, but the graphitization degree of CNTs is relatively high. The Fe-Co-Ni catalysts has high catalytic efficiency but low graphitization degree of CNTs. The tensile strength of carbon fiber/CNTs reinforcements prepared by Fe-Ni catalysts at 400 °C is the highest, reaching 3.99 GPa, which is 11.14% higher than that of desized fiber. The melt drop phenomenon of the catalysts was found by TEM, indicating the formation of the liquid phase catalysts during the growth of CNTs. This phenomenon can change the diffusion mode of carbon atoms in the catalyst and significantly reduce the growth activation energy of CNTs, so that CNTs can grow at lower temperatures. Based on the detailed analysis of the CVD process, a low temperature growth model of CNTs on carbon fibers was proposed.
为了降低化学气相沉积(CVD)过程中高温对催化剂对碳纤维的刻蚀作用,采用了四种多元素催化剂,即Fe-Co、Fe-Ni、Co-Ni和Fe-Co-Ni,以实现碳纳米管(CNT)在350℃至400℃的碳纤维上低温生长。结果表明,碳纳米管的生长状态与催化剂类型有很大关系。Fe-Co催化剂的催化效率较低,但碳纳米管的石墨化程度相对较高。Fe-Co-Ni催化剂具有较高的催化效率,但碳纳米管的石墨化程度较低。400℃下由Fe-Ni催化剂制备的碳纤维/碳纳米管增强材料的拉伸强度最高,达到3.99 GPa,比脱浆纤维高11.14%。通过透射电子显微镜发现了催化剂的熔体滴落现象,表明在碳纳米管生长过程中形成了液相催化剂。这种现象可以改变碳原子在催化剂中的扩散方式,并显著降低碳纳米管的生长活化能,从而使碳纳米管能够在较低温度下生长。基于对CVD过程的详细分析,提出了碳纳米管在碳纤维上的低温生长模型。