A transformation of naphthalene-based coalescenced mesophase pitch(NMP)to mesophase microbeads was achieved by heating a mixture of NMP and fullerene(C_(60)).This is different from the conventional process of the liqu...A transformation of naphthalene-based coalescenced mesophase pitch(NMP)to mesophase microbeads was achieved by heating a mixture of NMP and fullerene(C_(60)).This is different from the conventional process of the liquid-phase carbonization of isotropic pitch to the emergence of carbon microbeads in the matrix and finally their growth to form a 100%anisotropic bulk meso-phase,but rather a reverse transformation.The effects of C_(60) loading and reaction temperature on the morphological transformation of mesophase were investigated by polarizing optical and scanning electron microscopies.The physical changes in the NMP induced by C_(60) were characterized by thermogravimetric analysis,Fourier transform infrared spectroscopy,X-ray diffractometry and Raman spectroscopy.The results show that the coalesced NMP can be converted to a spherical type at 300-320℃ with the addition of 5%C_(60),and the size of the mesophase microbeads increases with increasing temperature.Furthermore,a model is established to ex-plain the unique induction effect of C_(60) in the transformation process.This work makes the morphological transformation of MP con-trollable,and provides a new idea for the understanding and research of mesophase pitch.展开更多
Graphitized carbon foams(GFms)were prepared using mesophase pitch(MP)as a raw material by foaming(450℃),pre-oxidation(320℃),carbonization(1000℃)and graphitization(2800℃).The differences in structure and properties...Graphitized carbon foams(GFms)were prepared using mesophase pitch(MP)as a raw material by foaming(450℃),pre-oxidation(320℃),carbonization(1000℃)and graphitization(2800℃).The differences in structure and properties of GFms prepared from different MP precursors pretreated by ball milling or liquid phase extraction were investigated and compared,and semi-quantitative calculations were conducted on the Raman and FTIR spectra of samples at each preparation stage.Semi-quantitat-ive spectroscopic analysis provided detailed information on the structure and chemical composition changes of the MP and GFm de-rived from it.Combined with microscopic observations,the change from precursor to GFm was analyzed.The results showed that ball milling concentrated the distribution of aromatic molecules in the pitch,which contributed to uniform foaming to give a GFm with a uniform pore distribution and good properties.Liquid phase extraction helped remove light components while retaining large aromatics to form graphitic planes with the largest average size during post-treatment to produce a GFm with the highest degree of graphitization and the fewest open pores,giving the best compression resistance(2.47 MPa),the highest thermal conductivity(64.47 W/(m·K))and the lowest electrical resistance(13.02μΩ·m).Characterization combining semi-quantitative spectroscopic ana-lysis with microscopic observations allowed us to control the preparation of the MP-derived GFms.展开更多
Because of its high purity and excellent orientation, mesophase pitch is a superior precursor for high-performance car-bon materials. However, the preparation of top-notch mesophase pitch faces challenges. Catalytic p...Because of its high purity and excellent orientation, mesophase pitch is a superior precursor for high-performance car-bon materials. However, the preparation of top-notch mesophase pitch faces challenges. Catalytic polycondensation at low temperat-ures is more favorable for synthesizing mesophase pitch, because it circumvents the high-temperature free radical reaction of other thermal polycondensation approaches. The reaction is gentle and can be easily controlled. It has the potential to significantly im-prove the yield of mesophase pitch and easily introduce naphthenic characteristics into the molecules, catalytic polycondensation is therefore a preferred method of synthesizing highly spinnable mesophase pitch. This review provides a synopsis of the selective pre-treatment of the raw materials to prepare different mesophase pitches, and explains the reaction mechanism and associated research advances for different catalytic systems in recent years. Finally, how to manufacture high-quality mesophase pitch by using a cata-lyst-promoter system is summarized and proposed, which may provide a theoretical basis for the future design of high-quality pitch molecules.展开更多
The Neoproterozoic-Lower Paleozoic dolostone gas reservoirs in the Chuanzhong Uplift in Southwestern China contain the mesophase pyrobitumen (pyrobitumen with mesophase). The mesophase in the pyrobitumen is mostly com...The Neoproterozoic-Lower Paleozoic dolostone gas reservoirs in the Chuanzhong Uplift in Southwestern China contain the mesophase pyrobitumen (pyrobitumen with mesophase). The mesophase in the pyrobitumen is mostly composed of a mixture of condensed macromolecule polycyclic aromatic hydrocarbons (PAH), and has been mostly converted to various grain, flow, and domain textures. The volcanic activity nearby the Chuanzhong Uplift may have generated very hot (over 300 °C) hydrothermal fluid, with migration of the fluid into the dolostone reservoir transforming the hydrocarbons in the reservoir into an anisotropic carbon by-product, which formed under high temperature and pressure conditions;over 300 °C and 200 MPa according to fluid inclusion analysis. The high temperature-pressure in reservoir was caused by sudden devolatilization of the hydrocarbons due to hydrothermal heating, which formed the unusual texture of the mesophase. The elliptical mesophase grains (EG), the honeycomb structure of pyrobitumen, and the occurrence of polarized classes of mesophase in single pyrobitumen deposits are all unusual textures. This study investigates the texture development of this pressure-affected pyrobitumen. Observation and study of the mesophase suggest that the class of mesophase in pyrobitumen is determined by temperature, while pressure (assessed from associated fluid inclusions) significantly affected the texture. Analysis of the texture of the pyrobitumen in conjunction with previous thermometry results from methane inclusions suggests that the high class mesophase of the pyrobitumen could be applied as a temperature indicator for geological conditions. Furthermore, the unusual textures of the pyrobitumen including elliptical mesophase grains (EG), the honeycomb structure of pyrobitumen, and the occurrence of polarized classes of mesophase in single pyrobitumen could reflect the abnormal high formation pressure.展开更多
In order to obtain the microwave absorption(MA)materials with light weight,high efficiency and tunable properties,the carbonized mesophase pitch(CMP)with the variation in carbonization temperatures and particle sizes ...In order to obtain the microwave absorption(MA)materials with light weight,high efficiency and tunable properties,the carbonized mesophase pitch(CMP)with the variation in carbonization temperatures and particle sizes were prepared and characterized.The carbonization temperature mainly controlled the graphitization degree of the CMP to affect their conductive loss.The carbon residues were generated on the CMP surface when the temperature was higher than 700℃,which contributed significantly to the polarization loss of the CMP.For scale regulation,the segregation between the particles in the paraffin ring caused by the reduction particles of CMP carbonization at 750℃(750 CMP)resulted in a significant reduction in conductive losses while improving their impedance matching.The 750 CMP over 300 mesh sieved had the strongest MA properties of-53 d B at 3.4 GHz within 5.5 mm.Moreover,the prepared CMPs were multi-layer compounded and optimized by CST microwave studio.The synergistic effect derived from the improved impedance matching and the enhanced interfacial polarization resulted in significant reflection loss in multi-layer CMP.Overall,these findings lead to the systematically regulation of carbon-based materials for MA,showing an attractive application prospect for the preparation of high-performance MA materials.展开更多
Mesocarbon microbeads （MCMB） were prepared from coal tar pitch modified by phenolic resin and from the same pitch modified by phenolic resin and hexamethylenetetramine at 440℃ for lh. By investigating the morpholog...Mesocarbon microbeads （MCMB） were prepared from coal tar pitch modified by phenolic resin and from the same pitch modified by phenolic resin and hexamethylenetetramine at 440℃ for lh. By investigating the morphology of mesophase spheres and the structure of the MCMB carbonized at 1000℃ for lh using scanning electron microscope （SEM） and XRD, it was found that phenolic resin accelerated the formation and coalescence of mesophase spheres. Some of the obtained MCMB were hi- or tri-spheres with the distorted microtextural carbon layers. Hexamethylenetetramine in the pitch modified by phenolic resin accelerated the condensation of phenolic resin and consequently expedited the combination of mesophase spheres, which was proved by the formation of some tetra-spheres. Owing to the cross-linkage of the additives, MCMB with complex structure were obtained.展开更多
The influences of molar ratio of KOH to C and activated temperature on the pore structure and electrochemical property of porous activated carbon from mesophase pitch activated by KOH were investigated. The surface ar...The influences of molar ratio of KOH to C and activated temperature on the pore structure and electrochemical property of porous activated carbon from mesophase pitch activated by KOH were investigated. The surface areas and the pore structures of activated carbons were analyzed by nitrogen adsorption, and the electrochemical properties of the activated carbons were studied using two-electrode capacitors in organic electrolyte. The results indicate that the maximum surface area of 3 190 m2/g is obtained at molar ratio of KOH to C of 5:1, the maximum specific capacitance of 122 F/g is attained at molar ratio of KOH to C of 4:1, and 800 ℃ is the proper temperature to obtain the maximum surface area and capacitance.展开更多
Molecular simulations were performed to investigate the molecular structural effects on needle coke mesophase stacking.The simulation results showed that the stacking states of anthracene trimer and tetramer accumulat...Molecular simulations were performed to investigate the molecular structural effects on needle coke mesophase stacking.The simulation results showed that the stacking states of anthracene trimer and tetramer accumulations were orderly,while the stacking states of anthracene dimer,pentamer,and hexamer accumulations were disorderly.Anthracene trimer and tetramer in the model compounds were two of the most ideal needle coke mesophase constituents.It was also found that the introduction of methyl side chains in anthracene trimer derivatives was not conducive to the formation of a mesophase crystal.To sum up,the molecules which had similar structures to anthracene trimer or tetramer with no alkyl chains are ideal constituents of needle coke mesophase.展开更多
文摘A transformation of naphthalene-based coalescenced mesophase pitch(NMP)to mesophase microbeads was achieved by heating a mixture of NMP and fullerene(C_(60)).This is different from the conventional process of the liquid-phase carbonization of isotropic pitch to the emergence of carbon microbeads in the matrix and finally their growth to form a 100%anisotropic bulk meso-phase,but rather a reverse transformation.The effects of C_(60) loading and reaction temperature on the morphological transformation of mesophase were investigated by polarizing optical and scanning electron microscopies.The physical changes in the NMP induced by C_(60) were characterized by thermogravimetric analysis,Fourier transform infrared spectroscopy,X-ray diffractometry and Raman spectroscopy.The results show that the coalesced NMP can be converted to a spherical type at 300-320℃ with the addition of 5%C_(60),and the size of the mesophase microbeads increases with increasing temperature.Furthermore,a model is established to ex-plain the unique induction effect of C_(60) in the transformation process.This work makes the morphological transformation of MP con-trollable,and provides a new idea for the understanding and research of mesophase pitch.
文摘Graphitized carbon foams(GFms)were prepared using mesophase pitch(MP)as a raw material by foaming(450℃),pre-oxidation(320℃),carbonization(1000℃)and graphitization(2800℃).The differences in structure and properties of GFms prepared from different MP precursors pretreated by ball milling or liquid phase extraction were investigated and compared,and semi-quantitative calculations were conducted on the Raman and FTIR spectra of samples at each preparation stage.Semi-quantitat-ive spectroscopic analysis provided detailed information on the structure and chemical composition changes of the MP and GFm de-rived from it.Combined with microscopic observations,the change from precursor to GFm was analyzed.The results showed that ball milling concentrated the distribution of aromatic molecules in the pitch,which contributed to uniform foaming to give a GFm with a uniform pore distribution and good properties.Liquid phase extraction helped remove light components while retaining large aromatics to form graphitic planes with the largest average size during post-treatment to produce a GFm with the highest degree of graphitization and the fewest open pores,giving the best compression resistance(2.47 MPa),the highest thermal conductivity(64.47 W/(m·K))and the lowest electrical resistance(13.02μΩ·m).Characterization combining semi-quantitative spectroscopic ana-lysis with microscopic observations allowed us to control the preparation of the MP-derived GFms.
文摘Because of its high purity and excellent orientation, mesophase pitch is a superior precursor for high-performance car-bon materials. However, the preparation of top-notch mesophase pitch faces challenges. Catalytic polycondensation at low temperat-ures is more favorable for synthesizing mesophase pitch, because it circumvents the high-temperature free radical reaction of other thermal polycondensation approaches. The reaction is gentle and can be easily controlled. It has the potential to significantly im-prove the yield of mesophase pitch and easily introduce naphthenic characteristics into the molecules, catalytic polycondensation is therefore a preferred method of synthesizing highly spinnable mesophase pitch. This review provides a synopsis of the selective pre-treatment of the raw materials to prepare different mesophase pitches, and explains the reaction mechanism and associated research advances for different catalytic systems in recent years. Finally, how to manufacture high-quality mesophase pitch by using a cata-lyst-promoter system is summarized and proposed, which may provide a theoretical basis for the future design of high-quality pitch molecules.
基金funded by the National Natural Science Foundation of China for Young Scholars(No.41903059).
文摘The Neoproterozoic-Lower Paleozoic dolostone gas reservoirs in the Chuanzhong Uplift in Southwestern China contain the mesophase pyrobitumen (pyrobitumen with mesophase). The mesophase in the pyrobitumen is mostly composed of a mixture of condensed macromolecule polycyclic aromatic hydrocarbons (PAH), and has been mostly converted to various grain, flow, and domain textures. The volcanic activity nearby the Chuanzhong Uplift may have generated very hot (over 300 °C) hydrothermal fluid, with migration of the fluid into the dolostone reservoir transforming the hydrocarbons in the reservoir into an anisotropic carbon by-product, which formed under high temperature and pressure conditions;over 300 °C and 200 MPa according to fluid inclusion analysis. The high temperature-pressure in reservoir was caused by sudden devolatilization of the hydrocarbons due to hydrothermal heating, which formed the unusual texture of the mesophase. The elliptical mesophase grains (EG), the honeycomb structure of pyrobitumen, and the occurrence of polarized classes of mesophase in single pyrobitumen deposits are all unusual textures. This study investigates the texture development of this pressure-affected pyrobitumen. Observation and study of the mesophase suggest that the class of mesophase in pyrobitumen is determined by temperature, while pressure (assessed from associated fluid inclusions) significantly affected the texture. Analysis of the texture of the pyrobitumen in conjunction with previous thermometry results from methane inclusions suggests that the high class mesophase of the pyrobitumen could be applied as a temperature indicator for geological conditions. Furthermore, the unusual textures of the pyrobitumen including elliptical mesophase grains (EG), the honeycomb structure of pyrobitumen, and the occurrence of polarized classes of mesophase in single pyrobitumen could reflect the abnormal high formation pressure.
基金supported by Sichuan Science and Technology Program,Grant No.2022YFG0111the Postdoctoral Innovative Talent Support Program(Grant No.BX20190220)the State Key Laboratory of Polymer Materials Engineering(Grant No.sklpme2019-2-02)for financial support。
文摘In order to obtain the microwave absorption(MA)materials with light weight,high efficiency and tunable properties,the carbonized mesophase pitch(CMP)with the variation in carbonization temperatures and particle sizes were prepared and characterized.The carbonization temperature mainly controlled the graphitization degree of the CMP to affect their conductive loss.The carbon residues were generated on the CMP surface when the temperature was higher than 700℃,which contributed significantly to the polarization loss of the CMP.For scale regulation,the segregation between the particles in the paraffin ring caused by the reduction particles of CMP carbonization at 750℃(750 CMP)resulted in a significant reduction in conductive losses while improving their impedance matching.The 750 CMP over 300 mesh sieved had the strongest MA properties of-53 d B at 3.4 GHz within 5.5 mm.Moreover,the prepared CMPs were multi-layer compounded and optimized by CST microwave studio.The synergistic effect derived from the improved impedance matching and the enhanced interfacial polarization resulted in significant reflection loss in multi-layer CMP.Overall,these findings lead to the systematically regulation of carbon-based materials for MA,showing an attractive application prospect for the preparation of high-performance MA materials.
基金Supported by the National Natural Science Foundation of China (No.50172034).
文摘Mesocarbon microbeads （MCMB） were prepared from coal tar pitch modified by phenolic resin and from the same pitch modified by phenolic resin and hexamethylenetetramine at 440℃ for lh. By investigating the morphology of mesophase spheres and the structure of the MCMB carbonized at 1000℃ for lh using scanning electron microscope （SEM） and XRD, it was found that phenolic resin accelerated the formation and coalescence of mesophase spheres. Some of the obtained MCMB were hi- or tri-spheres with the distorted microtextural carbon layers. Hexamethylenetetramine in the pitch modified by phenolic resin accelerated the condensation of phenolic resin and consequently expedited the combination of mesophase spheres, which was proved by the formation of some tetra-spheres. Owing to the cross-linkage of the additives, MCMB with complex structure were obtained.
基金Project(06FJ4059) supported by Hunan Provincial Academician Foundation
文摘The influences of molar ratio of KOH to C and activated temperature on the pore structure and electrochemical property of porous activated carbon from mesophase pitch activated by KOH were investigated. The surface areas and the pore structures of activated carbons were analyzed by nitrogen adsorption, and the electrochemical properties of the activated carbons were studied using two-electrode capacitors in organic electrolyte. The results indicate that the maximum surface area of 3 190 m2/g is obtained at molar ratio of KOH to C of 5:1, the maximum specific capacitance of 122 F/g is attained at molar ratio of KOH to C of 4:1, and 800 ℃ is the proper temperature to obtain the maximum surface area and capacitance.
基金Funding provided by the Molecular Simulation Key Laboratory at SINOPEC Research Institute of Petroleum Processing is gratefully acknowledged.
文摘Molecular simulations were performed to investigate the molecular structural effects on needle coke mesophase stacking.The simulation results showed that the stacking states of anthracene trimer and tetramer accumulations were orderly,while the stacking states of anthracene dimer,pentamer,and hexamer accumulations were disorderly.Anthracene trimer and tetramer in the model compounds were two of the most ideal needle coke mesophase constituents.It was also found that the introduction of methyl side chains in anthracene trimer derivatives was not conducive to the formation of a mesophase crystal.To sum up,the molecules which had similar structures to anthracene trimer or tetramer with no alkyl chains are ideal constituents of needle coke mesophase.
