The spherical mesophases are the main precursors for the high tap density of carbonaceous anode batteries. However, it is challenging to control mesophase size without coalescence and no deformation since it quickly coalesces into a regular large sphere. Here, we propose a feasible extraction method to refine the spherical size of mesophase using benzene. Thermogravimetric and differential scanning calorimetry analysis of untreated pitch revealed that the maximum temperature for mesophase nucleation should not exceed 410 °C to provoke the nucleation of mesophase spheres while maintaining a high pyrolysis yield. The extraction results showed that the extraction weight tends to decrease with an increase in the solvent ratio. There is an exponential relationship between the influence of solvent ratio and the ability for extraction. The solubility of the spherical mesophase in benzene is size-dependent and can dissolve selectively spherical mesophases smaller than 5 μm. Consequently, a monodisperse spherical mesophase was obtained. The reason for forming uniform mesophase spheres can be explained by their thermodynamic state, as described by the “two-step” classical nucleation theory. Benzene effectively improves the size distribution of spherical mesophase by dissolving small sizes while retaining large ones.

Mesophase pitch is a unique graphitizable material that has been used as an important precursor for highly graphitic carbon materials. In the current study, we propose to consider a spinnable mesophase pitch as a lyotropic liquid crystalline solution composed of solvent components and liquid crystalline components, so-called mesogen or mesogenic components. Among mesophase pitches, the supermesophase pitch is defined as a mesohpase pitch with 100% anisotropy, and can only be observed in pitches with a proportion of mesogenic components exceeding the threshold concentration (TC). We also examined the critical limit of AR synthetic pitch and 5 experimental spinnable mesophase pitches (SMPs). Then, we examined the effect of the solvent component on the minimum required amount of mesogenic component using a selected solvent component instead of their own solvent components. AR pitch showed 100% anisotropy with the least amount of its mesogenic component, THF insoluble components, of 60 wt.%. The solvent component, THF soluble components, extracted from AR-pitch, which has a molecular weight pattern similar to that of the original material but more amount of naphthenic alkyl chains, showed better solvent functionality than those of other THF solubles (THFSs) from other as-prepared spinnable mesophase pitches. This is why a lower amount of AR THFS can produce a supermesophase pitch when combined with the THFI (mesogenic components) of other experimental mesophase pitches. As a result of the current analysis, we define the mesogens as molecules that not only readily stack, but also maintain stacking structures in a fused state in the solution. The solvent component, on the other hand, is defined as molecules with a structure that readily decomposes in a fused state in the solution.

The facile production of high-purity mesophase pitch has been a long-standing desire in various carbon industries. Recently, polymer additives for mesophase production have attracted much attention because of their convenience and efficiency. We propose polyvinylidene fluoride (PVDF) as a strong candidate as an effective additive for mesophase production. The mesophase content and structural, chemical, and thermal properties of pitches obtained with different amounts of added PVDF are discussed. The influence of PVDF decomposition on mesophase formation is also discussed. We believe that this work provides an effective option for mesophase pitch production.

Spinnable mesophase pitch precursor containing more than 98% mesophase content was successfully prepared from FCC-DO (fluid catalytic cracking-decant oil) without hydrogenation or catalytic reaction. The preparation method involved thermal condensation, vacuum treatment, and annealing treatment. Petroleum mesophase pitch-based carbon fibers are produced by melt spinning of pitch precursors, followed by stabilization and carbonization. The resulting carbon fiber exhibited good mechanical performances up to tensile strength of 2.1 GPa and tensile modulus of 212 GPa, with strain-to-failure higher than 1.0%. These properties ensuring that the automotive grade carbon fibers can be successfully prepared from FCC-DO derived petroleum mesophase pitches through the cost-competitive processes.

Structural characterization of pyrolysis fuel oil (PFO) was conducted via 1H NMR and 13C NMR to elucidate its molecular structure and evaluate the feasibility of using PFO as a raw material for mesophase pitch synthesis. The average structural parameters were calculated based on the data from elemental analysis and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS), as well as 1H NMR and 13C NMR data. The resultant structural features of PFO were compared with those of fluidized catalytic cracking-decant oil (FCC-DO). Based on the calculated parameters, we proposed average molecular models of PFO and FCC-DO. The molecular model of PFO showed that it had an aromatic structure consisting of three aromatic rings and one naphthenic ring fused with one pericondensed and two catacondensed aromatic carbons, as well as a short alkyl side chain (with only a methyl group). This structural feature of PFO demonstrated that it is highly favorable for use as a raw material for mesophase pitch synthesis. The empirical findings in this study provide an in-depth understanding of the molecular structure of PFO as well as FCC-DO and can offer insights for future research on the utilization of PFO and other petroleum heavy oils.

The mesophase pith was synthesized based on effects of a high-pressure thermal condensation and feed (PFO/FCC-DO) blending. The reaction conditions were designed by fluidity and reactivity of each feed during the thermal reaction. The high-pressure thermal condensation process disturbs distillation of the volatile compounds in pyrolysis fuel oil (PFO); the fluidity can be controlled. In the blending process, PFO, which has a high thermal condensation reactivity, and fluid catalytic cracking-decant oil (FCC-DO), which maintains fluidity, interacted with a synergistic effect. Thus, mesophase pitch with a large mesophase content was manufactured by the two above processes.

We demonstrated an effective way of preparing melt spinnable mesophase pitches via catalytic hydrogenation of petroleum residue (fluidized catalytic cracking-decant oil) and their subsequent thermal soaking. The mesophase pitches thus obtained were analyzed in terms of their viscosity, elemental composition, solubility, molecular weight, softening point and optical texture. We found that zeolite-induced catalytic hydrogenation under high hydrogen pressure contributed to a large variation in the properties of the pitches. As the hydrogen pressure increased, the C/H ratio decreased, and the solubility in n-hexane increased. The mesophase pitch with entirely anisotropic domains of flow texture exhibited good meltspinnability. The mesophase carbon fibers obtained from the catalytically hydrogenated petroleum residue showed moderate mechanical properties.

This research considers the effect of added mesophase pitch (MP) as an additive during the pitch synthesis reaction of pyrolyzed fuel oil (PFO). Two effects are generated by adding MP. One is an enhancement of thermal stability due to the high thermal property of the additive; the other is that the volatile compounds that were removed by vaporization of PFO during the thermal reaction can participate in the pitch synthesis reaction (PFO→pitch) more efficiently. The effect differs according to the amount of the additive. When the amount of the additive is less than 7 wt%, the first effect is dominant, whereas the second effect is dominant when the additive amount exceeds 10 wt%.

Taguchi’s experimental design was employed in the melt spinning of molten mesophase pitch to produce carbon fibers. The textures of the obtained carbon fibers were radial with varied crack angles, as observed by scanning electron microscopy and polarized optical imaging. The diameter, crack angle, preferred orientation, and tensile modulus of the produced samples were examined to investigate the influence of four spinning variables. The relative importance of the variables has been emphasized for each characteristic. The results show that thicker carbon fiber can be obtained with a smaller entry angle, a higher spinning temperature, a reduced winding speed, and an increased extrusion pressure. The winding speed was found to be the most significant factor in relation to the fiber diameter. While it was observed that thicker carbon fiber generally shows improved preferred orientation, the most important variable affecting the preferred orientation was found to be the entry angle. As the entry angle decreased from 120° to 60°, the shear flow was enhanced to induce more ordered radial alignment of crystallite planes so as to obtain carbon fibers with a higher degree of preferred orientation. As a consequence, the crack angle was increased, and the tensile modulus was improved.

In this study, AR (aromatic resin) pitch was employed as the matrix-precursor for carbon/carbon composite because it exhibits much higher coke yield than coal tar pitch. As a result, a fabrication process of carbon/carbon composites can be shortened. It has been known that the pitches may cause swolling problem during the carbonization process. In order to restrain the swelling occurrence, a small quantity of carbon black was added to the AR pitch. Due to addition of carbon black the swelling was decreased largely and the perform can be infiltrated with the AR pitch. The densification efficiency of the performs was compared with various matrix-precursors. The coke yield of matrixprecursors, the morphology and the degree of graphitization of carbon matrix were analyzed.

Partial mesophase (PM) pitch precursor was prepared from fluidized catalytic cracking-decant oils (FCC-DO) by chemical reaction in the presence of Br2. The PM pitch heated-treatment at 420℃ for 9 h exhibited the softening point of 297℃ with 23% yield, and 55% anisotropic content. The PM pitch precursor was melt-spun through circular nozzle by pressurized N2, stabilized at 310℃, carbonized at 700℃, 1000℃, and 1200℃. The enough stabilization introduced 16.4% of the oxygen approximately. The stacking height (Lc002) and interlayer spacing (d002) of the as-spun fibers were 4.58 nm and 3.45a and the value became minimum and maximum at 700℃ respectively in the carbonization procedure. The tensile strength increased with an increase in the heat treatment temperature exhibiting highest value of 750 MPa at 1200℃ carbonization.

The C-type mesophase pitch-based carbon fiber (C-MPCF) was prepared throuch C-type spinnerette and compared the mechanical properties to those of round type mesophase pitch fiber (R-MPCF) and C-type isotropic pitch fiber (C-iPCF). The tensile strength and modulus of C-MPCF were about 18.6% and 35.7% higher than those of R-MPCF. The tensile strength of C-MPCF was 62% higher than that of C-iPCF of the same 8μm thickness because of more linear transverse texture, which could be easily converted to graphitic crystallinity during heat treatment. The torsional rigidity of C-MPCF was 2.37 times higher than that of R-MPCF. The electrical resistivity of C-MPCF was 8μΩ·m. The C-iPCF shows far lower electrical resistivity than R-iPCF as well as the mesophase carbon fiber because of better alignment of texture to the fiber axis.