The development of materials with excellent microwave absorption(MWA)and electromagnetic interference(EMI)shielding performances has currently received attention.Herein,mesophase pitch-based carbon foam(MPCF)with 3D i...The development of materials with excellent microwave absorption(MWA)and electromagnetic interference(EMI)shielding performances has currently received attention.Herein,mesophase pitch-based carbon foam(MPCF)with 3D interconnected pore structure was prepared through the high pressure pyrolysis of mesophase coal tar pitch.It is found that the 3D interconnected cellular pores of MPCF facilitate multiple reflections of electromagnetic waves,which results in the minimum reflection loss(RLmin)value of MPCF reaches-37.84 dB with the effective absorption bandwidth(EAB)of 5.44 GHz at a thickness of 2.70 mm,and the total average electromagnetic shielding effectiveness(SE_(T))under 3.00 mm thickness achieves 26.52 dB in X-band.Subsequently,MPCF is activated by KOH to obtain activated carbon foam(A-MPCF).The average SE_(T)of A-MPCF achieves 103.00 dB for abundant nanopores on the pore cell walls,which leads to a transition from the multiple reflections of electromagnetic waves on the walls to diffuse reflection.Unfortunately,the reflection coefficient(R)of A-MPCF increases from 0.78 to 0.90.To reduce the R value,Fe_(3)O_(4)/A-MPCF was fabricated via the in situ growth of nano Fe_(3)O_(4)on A-MPCF.Consequently,the R value of Fe_(3)O_(4)/A-MPCF was reduced from 0.90 to 0.74,whereas the MWA performance was only slightly decreased.This work proposes a simple strategy for simultaneously adjusting MWA and EMI shielding performances of materials.展开更多
Mesophase pitch carbon fibers have an ultra-high modulus and thermal conductivity that are unmatched by other carbon fibers,making it irreplaceable in many fields.However,due to the high temperature dependence of the ...Mesophase pitch carbon fibers have an ultra-high modulus and thermal conductivity that are unmatched by other carbon fibers,making it irreplaceable in many fields.However,due to the high temperature dependence of the viscosity of the melted pitch and the poor mechanical properties of pitch fibers,it is difficult to reduce the fiber diameter when using continuous spinning.We used the Mathworks Matlab software to optimize the mesophase pitch melt spinning model and to simulate the effects of spinning temperature,mass flow rate,winder speed,and quenching air temperature near the spinneret on the maximum shear rate during drawing.Simulation results demonstrate that applying gradient cooling to the melt upon exiting the spinneret significantly reduces the maximum shear rate and extends the drawing zone,thereby promoting the spinning stability and helping reduce the fiber diameter.In the experiment,instead of quenching in air,we applied gradient cooling to the melt,whose temperature decreased according to the equation Ta=298+278exp(−11.4z),where Ta is the final air temperature in Kelvin,and z is the distance from the spinneret in meters.It was found the gradient cooling greatly improved the draw-down ratio,reducing the average diameter of the pitch fibers from 20.8 to 13.1μm,along with improved process stability.The experimental results are in excellent agreement with the predictions.At the same time,the tensile strength of the 1150°C carbonized fibers increased from 0.6 to 1.1 GPa.Although the degree of orientation of the fibers decreased slightly,the tight bonding between microcrystals,the suppression of splitting,and the smaller diameter improved the mechanical properties of carbon fibers.This study provides an effective method for reducing the fiber diameter while improving continuity.展开更多
Reducing the amount of aluminum chloride needed for the catalytic preparation of high quality mesophase and carbon materials is important and we have found that using terephthalic acid(PTA)as a co-catalyst serves this...Reducing the amount of aluminum chloride needed for the catalytic preparation of high quality mesophase and carbon materials is important and we have found that using terephthalic acid(PTA)as a co-catalyst serves this purpose.By adding 3%(mass fraction)AlCl_(3)and 0.9%(mass fraction)PTA to the coal tar pitch,approximately 90%mesophase was synthesized.The product(M-3-0.9)had a high stacking order(L_(c)=3.1 nm,n=10.14)and aromaticity(0.942).By adding PTA,a larger anisotropy content was produced using a smaller amount of AlCl_(3).The PTA participated in the polycondensation reaction through its own benzene ring structure to increase the catalytic activity.However,when its content was higher than 1.5%,the number of oxygen-containing groups in the product increased which was unfavorable for the aromatic lamellar stacking and gave rise to more isotropic structures.The work opens up a new way to prepare mesophase by a catalytic method.展开更多
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
A synthesis strategy of fluorescent carbon quantum dots(CQDs) with high quantum yield(QY) using aqua mesophase pitch(AMP) as the carbon source has been developed via the hydrothermal method in this study. The hydrothe...A synthesis strategy of fluorescent carbon quantum dots(CQDs) with high quantum yield(QY) using aqua mesophase pitch(AMP) as the carbon source has been developed via the hydrothermal method in this study. The hydrothermal temperature and soaking time have important effects on the morphology and QY of CQDs. As-prepared CQDs at 120℃ holding for 24 h(CQDs-120-24) have the uniform size of about 2.8 nm, and the QY can reach 27.6%. The obtained CQDs are successfully modified with ammonia and thionyl chloride, respectively, and they exhibit an excellent photocatalytic performance on degrading rhodamine B(Rh B), methyl blue(MB) and indigo carmine(IC). Importantly, the degradation percentage of N-CQDs on Rh B under natural light for 4 h reaches 97% with the degradation rate constant of 0.02463 min^(-1) and it can maintain 93% after repetitively used 5 times. The results indicate that these as-prepared CQDs have the potential application in degrading organic dyes.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 structural transformation of mesophase to crystalline phase of strain-induced poly(L-lactic acid) has been investigated by differential scanning calorimetry(DSC) and in situ temperature dependent polarized Fourier...The structural transformation of mesophase to crystalline phase of strain-induced poly(L-lactic acid) has been investigated by differential scanning calorimetry(DSC) and in situ temperature dependent polarized Fourier transform infrared(FTIR) spectroscopy. It is found that, as the drawing temperature increases, melting of strain-induced mesophase in the heating process can remarkably interfere the crystallization behavior subsequently. Coupling with in situ polarized FTIR, from 60 °C to 76 °C, the mesophase melts partially rather than completely melting, and changes immediately to three-dimensional ordered structure. Of particular note, through monitoring the subtle spectral change in the critical phase transformation temperature from 60 °C to 64 °C, it is clearly demonstrated that relaxation of oriented amorphous chains initially takes place prior to the melting of mesophase.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
A series of carbonaceous mesophase spherule/activated carbon composites were prepared as anode materials for super lithium ion capacitors using carbonaceous mesophase spherules as the core materials and pitch as the a...A series of carbonaceous mesophase spherule/activated carbon composites were prepared as anode materials for super lithium ion capacitors using carbonaceous mesophase spherules as the core materials and pitch as the active carbon shell precursor.The structures of the composites were examined by scanning electron microscopy and X-ray diffractometry.The electrochemical performance was investigated in electric double layer capacitor and half-cell.The results show that,the composite exhibits good performance in both capacitor and battery with a high reversible capacity of 306.6 mA·h/g(0.2C) in the half-cell,along with a capacitance of 25.8 F/g in the capacitor when an optimum ratio of carbonaceous mesophase spherules to active carbon is adopted.The composite also shows a favorable rate performance and good cycle ability.A working model of this anode in super lithium ion capacitors was established.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 this work, waste-styrene-butadiene-rubber(WSBR)-modified petroleum-based mesophase asphalt was prepared through a co-carbonization process. The influence of contents of WSBR and carbonization temperature on the pro...In this work, waste-styrene-butadiene-rubber(WSBR)-modified petroleum-based mesophase asphalt was prepared through a co-carbonization process. The influence of contents of WSBR and carbonization temperature on the properties of mesophase asphalt was investigated. The chemical constituents,microstructure and thermal property of the samples were characterized. The results show that using WSBR as modifier can significantly promote the formation of mesophase. When the temperature is constant, the addition of WSBR results in more optically anisotropic crystal structure in the samples, and a better thermal stability. When the content of WSBR is invariable, with increasing temperature, the content of anisotropic structure in mesophase asphalt becomes higher and more uniform. The thermal stability of the samples is the best when WSBR content is 10 wt%.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
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
In the present work, the PLLA mesophase formation and its kinetics at the advent of a chain mobility accelerator (polyethylene glycol (PEG)) are investigated by wide angle X-ray diffraction (WAXD) and time-resol...In the present work, the PLLA mesophase formation and its kinetics at the advent of a chain mobility accelerator (polyethylene glycol (PEG)) are investigated by wide angle X-ray diffraction (WAXD) and time-resolved Fourier transform infrared spectroscopy (FTIR). It is interestingly found that the presence of PEG could accelerate the formation of PLLA mesophase notably due to the enhanced chain mobility, giving rise to a substantially reduced half time (t0.5) of PLLA mesophase formation from 129 min to 8 min. The Avrami exponents (n) for the kinetics of mesophase formation are -0.5 for neat PLLA and 1 for PLLA/PEG, respectively, indicating that 1D-rod growth through heterogeneous nucleation occurs during formation of PLLA mesophase. Tensile testing demonstrates that PLLA mesophase could increase the tensile strength and modulus but decrease the elongation at break.展开更多
By a polarized light optical microscopy with a hot stage, liquid phase nuclear magnetic resonance 13 C NMR and 1 H NMR, X ray diffractometry and scanning electron microscopy (SEM), the factors that affect the formatio...By a polarized light optical microscopy with a hot stage, liquid phase nuclear magnetic resonance 13 C NMR and 1 H NMR, X ray diffractometry and scanning electron microscopy (SEM), the factors that affect the formation of mesophase in C/C composites, such as pressure, quinoline insolubles (QI) and heterocylic compounds, were analyzed. Further, the graphitizability of the resultant carbon was discussed. The results indicate that to some degree, QI contents accelerate the formation of mesophase at atmospheric pressure; while at high pressure, the coalescence and growth of mesophase spherules are impeded and the resultant coke produced from higher QI content pitch is harder to be graphitized. This is in agreement with the transfer of microstructure from domain anisotropy to fine grained mosaics.展开更多
In the ethyl-cyanoethylcellulose ((E-CE)C)/dichloroacetic acid (DCA) cholesteric liquid crystalline solution, the hand-like texture is formed when the mesophase aggregates with the disk-like texture grow to big enough...In the ethyl-cyanoethylcellulose ((E-CE)C)/dichloroacetic acid (DCA) cholesteric liquid crystalline solution, the hand-like texture is formed when the mesophase aggregates with the disk-like texture grow to big enough and merge with each other with increasing concentration. The band-like texture is composed of parallel equidistant bright and dark alternative strips which are about 0.2-2.0 μm in width. In the band-like texture, the layers of ordered polymer chains are perpendicular to the solution film and the axes of helicoids are parallel to it. The width of the strips is different in different zones. Under the effect of an external magnetic field, the strips in the band-like texture first become wider and then narrower gradually.Moreover, the axes of helicoids in the (E-CE) C/DCA mesomorphic solution change from the direction normal to the magnetic field to the agreement with the magnetic field direction.展开更多
Two-dimensional FT-IR correlation spectroscopy was used to reveal the structural changes of isotactic polypropylene(iPP) mesophase during the heating process.The co-relationship among the regular helical bands of iP...Two-dimensional FT-IR correlation spectroscopy was used to reveal the structural changes of isotactic polypropylene(iPP) mesophase during the heating process.The co-relationship among the regular helical bands of iPP was discussed according to synchronous spectrum.The results show that the segments with different length-helixes were found to undergo a disordered process in the temperature range of 25-60 ℃.展开更多
In this work, the mesophase properties were tuned via mixing two discotic molecules with structural complementarity. Compared with the liquid crystalline hexakis(n-hexyloxy)triphenylene(H6TP)materials(columnar he...In this work, the mesophase properties were tuned via mixing two discotic molecules with structural complementarity. Compared with the liquid crystalline hexakis(n-hexyloxy)triphenylene(H6TP)materials(columnar hexagonal phase from 53 ℃ to 91 ℃), mesophase types as well as phase transition temperatures varied with the introduction of crystalline hexaazatriphenylene derivative(PBH)molecules. The introduction of less than 33% amount of PBH disrupted the columnar hexagonal phase formed by H6 TP remarkably, followed by the decreased clearing temperatures of liquid crystals. As the PBH amount was further increased, the destroyed columnar hexagonal phase was turned into the columnar rectangular phase, in which H6 TP and PBH molecules together formed the columnar mesophase. The formation of new mesophase contributed to the enlarged mesophase temperature(from44 ℃ to 144 ℃). We speculated that the alkyl chains interaction induced by the PBH component competed with the strong p–p stacking between H6 TP molecules, thus altering the liquid crystalline properties including mesophase types and phase transition temperatures.展开更多
There was phase separation between the anisotropic and isotropic phases in the ethyl-acetyl cellulose/dichloroacetic acid cholesteric liquid crystalline solutions .The textures of mesophase varied with the concentrati...There was phase separation between the anisotropic and isotropic phases in the ethyl-acetyl cellulose/dichloroacetic acid cholesteric liquid crystalline solutions .The textures of mesophase varied with the concentration. The mesophases could form the disc-like texture, oily streaks texture and texture of domains gathered randomly. In the first two textures the layers of the ordered molecular chain were perpendicular to the slide surface and the axes of the helical structure were parallel to the slide surface.展开更多
基金Supported by the National Natural Science Foundation of China(22378181).
文摘The development of materials with excellent microwave absorption(MWA)and electromagnetic interference(EMI)shielding performances has currently received attention.Herein,mesophase pitch-based carbon foam(MPCF)with 3D interconnected pore structure was prepared through the high pressure pyrolysis of mesophase coal tar pitch.It is found that the 3D interconnected cellular pores of MPCF facilitate multiple reflections of electromagnetic waves,which results in the minimum reflection loss(RLmin)value of MPCF reaches-37.84 dB with the effective absorption bandwidth(EAB)of 5.44 GHz at a thickness of 2.70 mm,and the total average electromagnetic shielding effectiveness(SE_(T))under 3.00 mm thickness achieves 26.52 dB in X-band.Subsequently,MPCF is activated by KOH to obtain activated carbon foam(A-MPCF).The average SE_(T)of A-MPCF achieves 103.00 dB for abundant nanopores on the pore cell walls,which leads to a transition from the multiple reflections of electromagnetic waves on the walls to diffuse reflection.Unfortunately,the reflection coefficient(R)of A-MPCF increases from 0.78 to 0.90.To reduce the R value,Fe_(3)O_(4)/A-MPCF was fabricated via the in situ growth of nano Fe_(3)O_(4)on A-MPCF.Consequently,the R value of Fe_(3)O_(4)/A-MPCF was reduced from 0.90 to 0.74,whereas the MWA performance was only slightly decreased.This work proposes a simple strategy for simultaneously adjusting MWA and EMI shielding performances of materials.
文摘Mesophase pitch carbon fibers have an ultra-high modulus and thermal conductivity that are unmatched by other carbon fibers,making it irreplaceable in many fields.However,due to the high temperature dependence of the viscosity of the melted pitch and the poor mechanical properties of pitch fibers,it is difficult to reduce the fiber diameter when using continuous spinning.We used the Mathworks Matlab software to optimize the mesophase pitch melt spinning model and to simulate the effects of spinning temperature,mass flow rate,winder speed,and quenching air temperature near the spinneret on the maximum shear rate during drawing.Simulation results demonstrate that applying gradient cooling to the melt upon exiting the spinneret significantly reduces the maximum shear rate and extends the drawing zone,thereby promoting the spinning stability and helping reduce the fiber diameter.In the experiment,instead of quenching in air,we applied gradient cooling to the melt,whose temperature decreased according to the equation Ta=298+278exp(−11.4z),where Ta is the final air temperature in Kelvin,and z is the distance from the spinneret in meters.It was found the gradient cooling greatly improved the draw-down ratio,reducing the average diameter of the pitch fibers from 20.8 to 13.1μm,along with improved process stability.The experimental results are in excellent agreement with the predictions.At the same time,the tensile strength of the 1150°C carbonized fibers increased from 0.6 to 1.1 GPa.Although the degree of orientation of the fibers decreased slightly,the tight bonding between microcrystals,the suppression of splitting,and the smaller diameter improved the mechanical properties of carbon fibers.This study provides an effective method for reducing the fiber diameter while improving continuity.
文摘Reducing the amount of aluminum chloride needed for the catalytic preparation of high quality mesophase and carbon materials is important and we have found that using terephthalic acid(PTA)as a co-catalyst serves this purpose.By adding 3%(mass fraction)AlCl_(3)and 0.9%(mass fraction)PTA to the coal tar pitch,approximately 90%mesophase was synthesized.The product(M-3-0.9)had a high stacking order(L_(c)=3.1 nm,n=10.14)and aromaticity(0.942).By adding PTA,a larger anisotropy content was produced using a smaller amount of AlCl_(3).The PTA participated in the polycondensation reaction through its own benzene ring structure to increase the catalytic activity.However,when its content was higher than 1.5%,the number of oxygen-containing groups in the product increased which was unfavorable for the aromatic lamellar stacking and gave rise to more isotropic structures.The work opens up a new way to prepare mesophase by a catalytic method.
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.
基金supported by the fund of the Beijing Laboratory for Food Quality and Safety, Beijing Technology and Business University (Grant No. FQS-201709)China Postdoctoral Science Foundation Funded Project (Grant No. 2016M592824)+1 种基金the Science and Technology Plan of Yulin City (Grant No. 2016-16-7)the Science and Technology Plan of Beilin District (Grant No. GX1710)
文摘A synthesis strategy of fluorescent carbon quantum dots(CQDs) with high quantum yield(QY) using aqua mesophase pitch(AMP) as the carbon source has been developed via the hydrothermal method in this study. The hydrothermal temperature and soaking time have important effects on the morphology and QY of CQDs. As-prepared CQDs at 120℃ holding for 24 h(CQDs-120-24) have the uniform size of about 2.8 nm, and the QY can reach 27.6%. The obtained CQDs are successfully modified with ammonia and thionyl chloride, respectively, and they exhibit an excellent photocatalytic performance on degrading rhodamine B(Rh B), methyl blue(MB) and indigo carmine(IC). Importantly, the degradation percentage of N-CQDs on Rh B under natural light for 4 h reaches 97% with the degradation rate constant of 0.02463 min^(-1) and it can maintain 93% after repetitively used 5 times. The results indicate that these as-prepared CQDs have the potential application in degrading organic dyes.
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financial supports from the National Natural Science Foundation of China(Nos.21774068 and 21704053)Natural Science Foundation of Shandong Province(No.ZR2017BB069)
文摘The structural transformation of mesophase to crystalline phase of strain-induced poly(L-lactic acid) has been investigated by differential scanning calorimetry(DSC) and in situ temperature dependent polarized Fourier transform infrared(FTIR) spectroscopy. It is found that, as the drawing temperature increases, melting of strain-induced mesophase in the heating process can remarkably interfere the crystallization behavior subsequently. Coupling with in situ polarized FTIR, from 60 °C to 76 °C, the mesophase melts partially rather than completely melting, and changes immediately to three-dimensional ordered structure. Of particular note, through monitoring the subtle spectral change in the critical phase transformation temperature from 60 °C to 64 °C, it is clearly demonstrated that relaxation of oriented amorphous chains initially takes place prior to the melting of mesophase.
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Project(2007BAE12B00) supported by the National Key Technology R&D Program of ChinaProject(50974136) supported by the National Natural Science Foundation of China
文摘A series of carbonaceous mesophase spherule/activated carbon composites were prepared as anode materials for super lithium ion capacitors using carbonaceous mesophase spherules as the core materials and pitch as the active carbon shell precursor.The structures of the composites were examined by scanning electron microscopy and X-ray diffractometry.The electrochemical performance was investigated in electric double layer capacitor and half-cell.The results show that,the composite exhibits good performance in both capacitor and battery with a high reversible capacity of 306.6 mA·h/g(0.2C) in the half-cell,along with a capacitance of 25.8 F/g in the capacitor when an optimum ratio of carbonaceous mesophase spherules to active carbon is adopted.The composite also shows a favorable rate performance and good cycle ability.A working model of this anode in super lithium ion capacitors was established.
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financially support provided by the National Natural Science Foundation of China (Grant No. 51772243)the Innovation Team Plan of Shaanxi Province (Grant No. 2017KCT-17)+1 种基金the China Postdoctoral Science Foundation Funded Project (Grant No. 2016M592824)the fund of the State Key Laboratory of Solidfication Processing in NWPU SKLSP201625
文摘In this work, waste-styrene-butadiene-rubber(WSBR)-modified petroleum-based mesophase asphalt was prepared through a co-carbonization process. The influence of contents of WSBR and carbonization temperature on the properties of mesophase asphalt was investigated. The chemical constituents,microstructure and thermal property of the samples were characterized. The results show that using WSBR as modifier can significantly promote the formation of mesophase. When the temperature is constant, the addition of WSBR results in more optically anisotropic crystal structure in the samples, and a better thermal stability. When the content of WSBR is invariable, with increasing temperature, the content of anisotropic structure in mesophase asphalt becomes higher and more uniform. The thermal stability of the samples is the best when WSBR content is 10 wt%.
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.
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financially supported by the National Natural Science Foundation of China(Nos.51120135002,51203104)the Doctoral Program of the Ministry of Education of China(No.20120181120101)+1 种基金the Program of Introducing Talents of Discipline to Universities(B13040)the Innovation Team Program of Science&Technology Department of Sichuan Province(No.2013TD0013)
文摘In the present work, the PLLA mesophase formation and its kinetics at the advent of a chain mobility accelerator (polyethylene glycol (PEG)) are investigated by wide angle X-ray diffraction (WAXD) and time-resolved Fourier transform infrared spectroscopy (FTIR). It is interestingly found that the presence of PEG could accelerate the formation of PLLA mesophase notably due to the enhanced chain mobility, giving rise to a substantially reduced half time (t0.5) of PLLA mesophase formation from 129 min to 8 min. The Avrami exponents (n) for the kinetics of mesophase formation are -0.5 for neat PLLA and 1 for PLLA/PEG, respectively, indicating that 1D-rod growth through heterogeneous nucleation occurs during formation of PLLA mesophase. Tensile testing demonstrates that PLLA mesophase could increase the tensile strength and modulus but decrease the elongation at break.
文摘By a polarized light optical microscopy with a hot stage, liquid phase nuclear magnetic resonance 13 C NMR and 1 H NMR, X ray diffractometry and scanning electron microscopy (SEM), the factors that affect the formation of mesophase in C/C composites, such as pressure, quinoline insolubles (QI) and heterocylic compounds, were analyzed. Further, the graphitizability of the resultant carbon was discussed. The results indicate that to some degree, QI contents accelerate the formation of mesophase at atmospheric pressure; while at high pressure, the coalescence and growth of mesophase spherules are impeded and the resultant coke produced from higher QI content pitch is harder to be graphitized. This is in agreement with the transfer of microstructure from domain anisotropy to fine grained mosaics.
基金This work was supported by Academia Sinica Selected Research Program.
文摘In the ethyl-cyanoethylcellulose ((E-CE)C)/dichloroacetic acid (DCA) cholesteric liquid crystalline solution, the hand-like texture is formed when the mesophase aggregates with the disk-like texture grow to big enough and merge with each other with increasing concentration. The band-like texture is composed of parallel equidistant bright and dark alternative strips which are about 0.2-2.0 μm in width. In the band-like texture, the layers of ordered polymer chains are perpendicular to the solution film and the axes of helicoids are parallel to it. The width of the strips is different in different zones. Under the effect of an external magnetic field, the strips in the band-like texture first become wider and then narrower gradually.Moreover, the axes of helicoids in the (E-CE) C/DCA mesomorphic solution change from the direction normal to the magnetic field to the agreement with the magnetic field direction.
基金financially supported by the National Natural Science Foundation of China(No.51373003)
文摘Two-dimensional FT-IR correlation spectroscopy was used to reveal the structural changes of isotactic polypropylene(iPP) mesophase during the heating process.The co-relationship among the regular helical bands of iPP was discussed according to synchronous spectrum.The results show that the segments with different length-helixes were found to undergo a disordered process in the temperature range of 25-60 ℃.
基金supported by the National Natural Science Foundation of China(No.51303177)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB12020300)
文摘In this work, the mesophase properties were tuned via mixing two discotic molecules with structural complementarity. Compared with the liquid crystalline hexakis(n-hexyloxy)triphenylene(H6TP)materials(columnar hexagonal phase from 53 ℃ to 91 ℃), mesophase types as well as phase transition temperatures varied with the introduction of crystalline hexaazatriphenylene derivative(PBH)molecules. The introduction of less than 33% amount of PBH disrupted the columnar hexagonal phase formed by H6 TP remarkably, followed by the decreased clearing temperatures of liquid crystals. As the PBH amount was further increased, the destroyed columnar hexagonal phase was turned into the columnar rectangular phase, in which H6 TP and PBH molecules together formed the columnar mesophase. The formation of new mesophase contributed to the enlarged mesophase temperature(from44 ℃ to 144 ℃). We speculated that the alkyl chains interaction induced by the PBH component competed with the strong p–p stacking between H6 TP molecules, thus altering the liquid crystalline properties including mesophase types and phase transition temperatures.
基金Projects supported by the Science Fund of the Chinese Academy of Sciences.
文摘There was phase separation between the anisotropic and isotropic phases in the ethyl-acetyl cellulose/dichloroacetic acid cholesteric liquid crystalline solutions .The textures of mesophase varied with the concentration. The mesophases could form the disc-like texture, oily streaks texture and texture of domains gathered randomly. In the first two textures the layers of the ordered molecular chain were perpendicular to the slide surface and the axes of the helical structure were parallel to the slide surface.