Formation of mesophase microbeads from bulk mesophase pitch induced by fullerene

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.

Semi-quantitative analysis of the structural evolution of mesophase pitch-based carbon foams by Raman and FTIR spectroscopy

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.

A review of the catalytic preparation of mesophase pitch

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.

基于Aqua卫星AIRS数据的南大洋大气逆温和逆湿特性研究

南大洋大气普遍存在着逆温和逆湿现象,其分布和变化对海-冰-气之间的物质和通量交换具有重要影响。利用Aqua卫星上搭载的大气红外探测器(AIRS)观测数据,提取了南大洋大气的逆温和逆湿特性,并研究了其时空分布与变化特征。此外,以全球无线电探空数据集的探测结果为参考值,分析了AIRS在进行大气逆温和逆湿探测过程中受到云量影响的特征。结果表明,AIRS估计的逆温特性受云量的影响较小,在多云条件下AIRS也可精确地估计逆温特性。利用AIRS最新的第7版(V7)数据产品对2004-2020年南大洋大气逆温和逆湿的频率(强度)进行研究,发现秋冬季比春夏季高(强),在龙尼冰架、罗斯冰架和南极半岛附近的海域的大气出现逆温和逆湿现象较其他区域更频繁,且强度更强。

Texture development of mesophase in reservoir pyrobitumen and the temperature-pressure converting of the gas reservoir in the Chuanzhong Uplift, Southwestern China

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.

Tunable and efficient microwave absorption from mesophase pitch carbide with designable electromagnetic properties

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.

HY1C/1D海表温度对Terra/Aqua产品的可替代性分析

通过卫星遥感获取的海表温度(SST)产品已经成为海洋和大气研究中的重要数据源,我国海洋水色遥感卫星(HY1C和HY1D)的海洋水色水温扫描仪(COCTS)具有两个热红外通道,可反演全球SST遥感产品。对比Terra和Aqua卫星的中分辨率成像光谱仪(MODIS)的SST产品,分析COCTS海表温度产品对MODIS相应产品的可替代性。比较了两种卫星的全球SST单日和月平均融合产品的图像空间结构,分析了匹配像元SST值的离散度,统计了HY1C/1D的误差结果,讨论了HY1C与HY1D产品的一致性、不同质量控制方案对SST产品影响以及遥感产品质量对昼夜SST变化研究影响等问题。结果表明,以2020年6月SST(Terra)为真值,HY1C白天SST的单日全球遥感产品的平均偏差、绝对偏差、均方根误差和相关系数分别为0.04℃、0.60℃、0.78℃和0.98,夜晚SST的单日全球遥感产品的平均偏差、绝对偏差、均方根误差和相关系数分别为-0.16℃、0.78℃、0.95℃和0.86。以2020年6月SST(Aqua)为真值,HY1D白天SST的单日全球遥感产品的平均偏差、绝对偏差、均方根误差和相关系数分别为0.02℃、0.59℃、0.79℃和0.98,夜晚SST的单日全球遥感产品的平均偏差、绝对偏差、均方根误差和相关系数分别为-0.09℃、0.61℃、0.82℃和0.96。这些统计值可以通过严格的质量控制方案来减小,但海洋锋面等区域的有效数据率会随着质量控制的阈值变小而显著减小。COCTS的全球SST遥感图像与MODIS相应产品在空间分布上差异性很小,长时间序列遥感图像结果比较具有良好的时空稳定性,多种SST产品整体都表现出对MODIS同类产品具有良好的一致性和可替代性。通过对SST昼夜变化等方面研究,提出了遥感SST产品质量提升的发展方向,来提高其在海洋昼夜温度短期变化等相关海洋学研究的应用能力。

Structural Characteristics of Mesophase Spheres Prepared from Coal Tar Pitch Modified by Phenolic Resin

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.

Mesophase formation of coal-tar pitches used for impregnant of C/C composites

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.

BAND-LIKE TEXTURE OF ETHYLCYANOETHYL CELLULOSE MESOPHASE

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.

Preparation of activated carbons from mesophase pitch and their electrochemical properties

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.

Evaluation of Molecular Structural Effects on Needle Coke Mesophase Stacking

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.

Carbonaceous mesophase spherule/activated carbon composite as anode materials for super lithium ion capacitors

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.

Modification of Mesophase Pitch from Petroleum Heavy Oils

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TEXTURES OF ETHYL-ACETYL CELLULOSE MESOPHASE

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.

THE STRUCTURES OF SOME MESOPHASE PITCH-BASED CARBON FIBRES

The macro-and micro-structure of two groups(high modulus and high thermalconductivity)of MP-based carbon fibres were studied using X-ray diffraction,and both scanningand transmission electron microscopy.The dominant macrostructure in cross section is of foldedpseudo-radial layers which have a tendency to form a quasi-uniform domain as the fibre modulusincreases.It is found that high thermal conductivity fibres have both missimg sector and circularcross sections(possessed predominantly by the high modulus fibre group).The microstructuralstudy indicates that apart from the fibre C700,which has a three-dimensional graphite structure,these two groups of carbon fibres all exhibit a turbostratic stacking order.Furthermore it is foundthat the turbostratic stacking thickness as determined from dark-field measurement is much largerthan the classical crystallite thickness L_c as measured from X-ray diffraction.

MORPHOLOGICAL STUDIES OF A THERMOTROPIC SIDE-CHAIN LIQUID CRYSTALLINE POLYMER DURING MESOPHASE TRANSITIONS

The morphological features of a side-chain liquid crystalline polymer during the mesophase transitions were investigated by using the DSC technique. The polymer used was polyacrylate with mesogens of three benzene rings attached to the main chain through a flexible spacer. A special two-phase texture was observed in the transition temperature range. Similar to main-chain liquid crystalline polymers the transition process of the side-chain liquid crystalline polymer was composed of an initiation of the new phase at local places of the old phase matrix and a growth process of the new phase domains.

KINETICS OF MESOPHASE FORMATION OF A LYOTROPIC AROMATIC POLYAMIDE

The kinetics of mesophase formation of a lyotropic aromatic polyamide from isotropic state has been studied by means of depolarized light intensity. Avrami type analysis of the data gives an exponent close to 1, which suggests the nucleation followed by one-dimensional growth. No influence of blending flexible chain from nylon 6 to the aromatic polyamide on the kinetics of mesophase formation was observed.

Comparative Study on Super Fine Mesophase Powder and MCMB Used to Manufacture High-Density Isotropic Carbon Bulks

Mesocarbon microbeads （MCMB） and super fine mesophase powder （SFMP） were prepared firstly from a coal tar pitch and then hot-condensed into high-density isotropic carbon （HDIC） bulks under 160 MPa and finally sintered at 1 000 ℃. By analyzing the thermogravimetric behavior of the MCMB and SFMP powders, their volume shrinkage and weight loss during sintering and the bulk density and flexural strengths of their sintered bulks, it was found that the smaller sizes and the richer β-resin contents of SFMP ha）re facilitated formation of sintered bulks with more compact isotropic structure and higher flexural strengths than MCMB. Because of the filling and bonding effects of SFMP on MCMB bulks, addition of SFMP, albeit a little, can greatly increase the flexural strengths of sintered bulks of MCMB. However, adding MCMB, even a slight amount, into SFMP can severely impair the flexural strength of sintered bulks. This might be attributed to both the crack initiation along the boundaries between MCMB and SFMP and the formation of layered texture of MCMB sphere.

Nature of the Supercritical Mesophase

It has been reported that at temperatures above the critical there is no “continuity of liquid and gas”, as originally hypothesized by van der Waals [1]. Rather, both gas and liquid phases, with characteristic properties as such, extend to supercritical temperatures [2]-[4]. Each phase is bounded by the locus of a percolation transition, i.e. a higher-order thermodynamic phase change associated with percolation of gas clusters in a large void, or liquid interstitial vacancies in a large cluster. Between these two-phase bounds, it is reported there exists a mesophase that resembles an otherwise homogeneous dispersion of gas micro-bubbles in liquid (foam) and a dispersion of liquid micro-droplets in gas (mist). Such a colloidal-like state of a pure one-component fluid represents a hitherto unchartered equilibrium state of matter besides pure solid, liquid or gas. Here we provide compelling evidence, from molecular dynamics (MD) simulations, for the existence of this supercritical mesophase and its colloidal nature. We report preliminary results of computer simulations for a model fluid using a simplistic representation of atoms or molecules, i.e. a hard-core repulsion with an attraction so short that the atoms are referred to as “adhesive spheres”. Molecular clusters, and hence percolation transitions, are unambiguously defined. Graphics of color-coded clusters show colloidal characteristics of the supercritical mesophase. We append this Letter to Natural Science with a debate on the scientific merits of its content courtesy of correspondence with Nature (Appendix).