Stabilization is the most complicated and time-consuming step in the manufacture of carbon fibers (CFs), which is important to prepare CFs with high performance. Accelerated stabilization was successfully demonstrated under effective plasma irradiation-assisted modification (PIM) of mesophase pitch fibers (PFs). The results showed that the PIM treatment could obviously introduce more oxygen-containing groups into PFs, which was remarkably efficient in shortening the stabilization time of PFs with a faster stabilization heating rate, as well as in preparing the corresponding CFs with higher performance. The obtained graphitized fiber (GF-5) from the PF-5 under PIM treatment of 5 min presented a higher tensile strength of 2.21 GPa, a higher tensile modulus of 502 GPa, and a higher thermal conductivity of 920 W/m·K compared to other GFs. Therefore, the accelerated stabilization of PFs by PIM treatment is an efficient strategy for developing low-cost pitch-based CFs with high performance.
Mesophase pitch is usually prepared by radical polymerization or catalytic polymerization from coal tar, petroleum, and aromatic compounds, and the catalytic synthesis of mesophase pitch from pure aromatic compounds is more controllable in the preparation of high-quality mesophase pitch. However, the corrosive and highly toxic nature of the catalyst has limited the further development of this method. In this study, mesophase pitch was synthetized using ethylene tar and naphthalene as raw materials and boron trifluoride diethyl etherate as a catalyst. The effect of the catalytic reaction on the structure and properties of the mesophase pitch was investigated. The results show that naphthalene plays an important role in the mesophase content and reaction pressure (from above 6 MPa to 2.35 MPa). Mesophase pitch with fine-flow texture can be prepared by introducing more methylene groups, naphthenic structures, and aliphatic hydrocarbons during synthesis. Carbon fibers prepared from mesophase pitch show a split structure, and the thermal conductivity is 730 W/(m·K). This work provides theoretical support for lower toxicity and causticity and for reaction-controlled technology for the synthesis of high-purity mesophase pitch.
The boron carbide (B4C) nanoparticles doping mesophase pitch (MP) was synthesized by the in-situ doping method with tetrahydrofuran solvent, and the corresponding MP−based carbon fibers (CFs) were successfully prepared through the melt−spinning, stabilization, carbonization and graphitization processes. The structural evolution and properties of boron−containing pitches and fibers in different processes were investigated for exploring the effect of B4C on mechanical, electrical and thermal properties of CFs. The results showed that the B4C was evenly dispersed in pitch fibers to provide active sites of oxygen, resulting in a homogeneous stabilization and ameliorating the split−ting microstructures of CFs. Moreover, the thermal conductivity of B1−MP−CF prepared with 1 wt.% B4C increased to 1051 W/m•K, which was much higher than that of B0−MP−CF prepared without B4C (659 W/m•K). While the tensile strength of B4C−doped CFs was lower than that of pristine CFs. In addition, a linear relationship equation between the graphite microcrystallite parameter (ID/IG) calculated from Raman spectra and the thermal conductivity (λ) calculated according to the electrical resistivity was found, which was beneficial to understand the thermal properties of CFs. Therefore, the doping B4C nanoparticles in MP did play a significant role in reducing the graphitization temperatures due to the boron catalytic graphitization but decreasing the mechanical properties due to the introduction of impurities.